Omniphobic polyurethane compositions, related articles, and related methods

ABSTRACT

The disclosure relates to a thermoset omniphobic composition, which includes a thermoset polymer with first, second, and third backbone segments, urethane groups linking the first and third backbone segments, and urea groups linking the first and second backbone segments. The first, second, and third backbone segments generally correspond to urethane or urea reaction products of polyisocyanate(s), amine-functional hydrophobic polymer(s), and polyol(s), respectively. The thermoset omniphobic composition has favorable omniphobic properties, for example as characterized by water and/or oil contact and/or sliding angles. The thermoset omniphobic composition can be used as a coating on any of a variety of substrates to provide omniphobic properties to a surface of the substrate. Such omniphobic coatings can be scratch resistant, ink/paint resistant, dirt-repellent, and optically clear. The thermoset omniphobic composition can be applied by different coating methods including cast, spin, roll, spray and dip coating methods.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation Application of U.S. application Ser.No. 16/764,255, filed May 14, 2020, which is a National Stageapplication of International Application No. PCT/US2018/061189, filedNov. 15, 2018, which claims the benefit of U.S. Provisional ApplicationNo. 62/586,430 (filed Nov. 15, 2017) and U.S. Provisional ApplicationNo. 62/727,215 (filed Sep. 5, 2018), which are incorporated herein byreference in their entireties.

STATEMENT OF GOVERNMENT INTEREST

None.

BACKGROUND OF THE DISCLOSURE Field of the Disclosure

The disclosure relates to a thermoset omniphobic composition (such as anomniphobic polyurethane composition) which includes a thermoset polymerwith first, second, and third backbone segments, urethane groups linkingthe first and third backbone segments, and urea groups linking the firstand second backbone segments. The first, second, and third backbonesegments generally correspond to urethane or urea reaction products ofpolyisocyanate(s), amine-functional hydrophobic polymer(s), andpolyol(s), respectively.

Brief Description of Related Technology

When water accumulates on a surface, the surface energy of the materialis directly related to how the water will react. Some surfaces may allowthe water to spread out into a pool with a large surface area, whereasothers may make water bead up into droplets. The contact angle betweenthe water droplet and the surface is used to characterize the surfaceinto three categories: hydrophilic (<90°), hydrophobic (90°-150°), andsuperhydrophobic (>150°). FIG. 1 is a visual representation of a contactangle measurement.

Hydrophobicity can be achieved in two ways: controlling the chemicalinteractions between water and the material surface or altering thesurface of the material. Generally, non-polar molecular groups areresponsible water beading on a surface as opposed to spreading, due tothe lower surface energies exhibited by non-polar groups. A lowersurface energy of the material will directly relate to a high contactangle. In contrast, high-energy materials will cause water to spread outin a thin pool, as the polar groups present in surfaces with highenergies attract the polar water molecules.

Physically altering the surface (e.g., increasing the roughness thereof)of the material may also increase the hydrophobicity of a material. Bycreating pillars or other similar features on a textured surface, waterinteracts with an increased surface area on the material, thusamplifying the chemical interactions between water and the surface. Animage depicting how texturing the surface leads to increased contactangle can be seen below in FIG. 2 .

A material that repels oils is known as oleophobic or lipophobicdepending on if the repelling action is a physical or chemical property,respectively, and operates analogously to hydrophobic materials. Thesematerials are often used on touch screen displays so that bodily oilsand sweat gland secretions do not build up on the surface of a screen. Amaterial that exhibits both hydrophobic and oleophobic properties isknown as omniphobic. Such materials with very high contact angles areoften regarded as “self-cleaning” materials, as contaminants willtypically bead up and roll off the surface. As such, these materialshave possible applications in screen display, window, and buildingmaterial coatings.

Hu et al. U.S. Publication No. 2016/0200937 discloses polyurethane-basedand epoxy-based compositions that be used as coatings and adhesives withabrasion-resistant, ink-resistant, anti-graffiti, anti-fingerprintproperties. The disclosed process for making the compositions requiresgraft and block copolymer components along with a two-step/two-potmanufacturing process, increasing the time to manufacture and cost ofthe product.

SUMMARY

In one aspect, the disclosure relates to a thermoset omniphobiccomposition comprising: a thermoset polymer comprising a crosslinkedbackbone, the crosslinked backbone comprising: (i) first backbonesegments (e.g., generally resulting from a polyisocyanate as describedbelow), (ii) second backbone segments (e.g., generally resulting from apolysiloxane or other hydrophobic polymer as described below), (iii)third backbone segments (e.g., generally resulting from a polyol asdescribed below), (iv) urethane groups linking first backbone segmentsand third backbone segments, and (v) urea groups linking first backbonesegments and second backbone segments; wherein: the first backbonesegments have a structure corresponding to at least one of a urethanereaction product and a urea reaction product from at least onepolyisocyanate (e.g., a diisocyanate, a triisocyanate, a mixture ofboth); the second backbone segments have a structure corresponding to aurea reaction product from at least one amine-functional hydrophobicpolymer having a glass transition temperature (T_(g)) of 50° C. or less;the third backbone segments have a structure corresponding to a urethanereaction product from at least one polyol; the urethane groups have astructure corresponding to a urethane reaction product of thepolyisocyanate and the polyol; and the urea groups have a structurecorresponding to a urea reaction product of the polyisocyanate and theamine-functional hydrophobic polymer.

Various refinements of the disclosed thermoset omniphobic compositionare possible.

In a refinement, the polyisocyanate comprises a diisocyanate. In anotherrefinement, the polyisocyanate comprises a triisocyanate. In anotherrefinement, the polyisocyanate comprises a biobased polyisocyanate. Inanother refinement, the polyisocyanate is selected from the groupconsisting of 1,5-naphthylene diisocyanate, 4,4′-diphenylmethanediisocyanate (MDI), hydrogenated MDI, xylene diisocyanate (XDI),tetramethylxylol diisocyanate (TMXDI), 4,4′-diphenyl-dimethylmethanediisocyanate, di- and tetraalkyl-diphenylmethane diisocyanate,4,4′-dibenzyl diiso-cyanate, 1,3-phenylene diisocyanate, 1,4-phenylenediisocyanate, one or more isomers of tolylene diisocyanate (TDI, such astoluene 2,4-diisocyanate), 1-methyl-2,4-diiso-cyanatocyclohexane,1,6-diisocyanato-2,2,4-trimethyl-hexane,1,6-diisocyanato-2,4,4-trimethylhexane,1-iso-cyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinatedand brominated diisocyanates, phosphorus-containing diisocyanates,4,4′-diisocyanatophenyl-perfluoroethane, tetramethoxybutane1,4-diisocyanate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate (orhexamethylene diisocyanate; HDI), HDI dimer (HDID), HDI trimer (HDIT),HDI biuret, dicyclohexylmethane diisocyanate, cyclohexane1,4-diisocyanate, ethylene diisocyanate, phthalic acidbisisocyanatoethyl ester, 1-chloromethylphenyl 2,4-diisocyanate,1-bromomethylphenyl 2,6-diisocyanate, 3,3-bischloromethyl ether4,4′-diphenyldiisocyanate, trimethylhexamethylene diisocyanate,1,4-diisocyanato-butane, 1,2-diisocyanatododecane, and combinationsthereof.

In a refinement, the amine-functional hydrophobic polymer is selectedfrom the group consisting of amine-functional polysiloxanes,amine-functional polyperfluoroethers, amine-functional polybutadienes,amine-functional polyisobutylene (“PIB”), amine-functional branchedpolyolefins, amine-functional polyacrylates and polymethacrylates (e.g.,also including C₂-C₁₆ pendant alkyl groups), and combinations thereof.In another refinement, the amine-functional hydrophobic polymercomprises a monoamine-functional polysiloxane. In another refinement,the amine-functional hydrophobic polymer comprises a diamine-functionalpolysiloxane. In another refinement, the amine-functional hydrophobicpolymer comprises an amine-functional polyperfluoroether. In anotherrefinement, the amine-functional hydrophobic polymer comprises anamine-functional polybutadiene. In another refinement, theamine-functional hydrophobic polymer comprises an amine-functionalpolyisobutene. In another refinement, the amine-functional hydrophobicpolymer comprises an amine-functional branched polyolefin. In anotherrefinement, the amine-functional hydrophobic polymer comprises anamine-functional poly(meth)acrylate. In another refinement,amine-functional polysiloxanes, amine-functional polyperfluoroethers,amine-functional polybutadienes, amine-functional polyisobutylene(“PIB”), amine-functional branched polyolefins, amine-functionalpolyacrylates and polymethacrylates, and other amine-functionalhydrophobic polymers can be used with a low melting melting point (e.g.,melting point from 0-60° C.) hydrophilic polymer/oligomer such asamine-functional poly(ethylene glycol) methyl ether (“PEO”).

In a refinement, the amine-functional hydrophobic polymer has a glasstransition temperature in a range from −150° C. to 50° C. In anotherrefinement, the amine-functional hydrophobic polymer is a liquid at atemperature in a range from −20° C. or 10° C. to 40° C.

In a refinement, the amine-functional hydrophobic polymer has amolecular weight ranging from 300 to 50,000 g/mol.

In a refinement, the polyol comprises a diol. In another refinement, thepolyol comprises a triol. In another refinement, the polyol comprisesthree or more hydroxyl groups. In another refinement, the polyolcomprises a biobased polyol. In another refinement, the polyol isselected from the group consisting of polyether polyols, hydroxlated(meth)acrylate oligomers, glycerol, ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol,1,4-butanediol, neopentyl glycol, 1,6-hexanediol,1,4-cyclohexanedimethanol, glycerol, trimethylolpropane,1,2,6-hexanetriol, pentaerythritol, (meth)acrylic polyols, polyesterpolyols, polyurethane polyols, and combinations thereof.

In a refinement, the first backbone segments are present in an amountranging from 10 wt. % to 90 wt. % relative to the thermoset polymer. Inanother refinement, the second backbone segments are present in anamount ranging from 0.01 wt. % to 20 wt. % relative to the thermosetpolymer. In another refinement, the third backbone segments are presentin an amount ranging from 10 wt. % to 90 wt. % relative to the thermosetpolymer.

In a refinement, the thermoset polymer crosslinked backbone furthercomprises: fourth backbone segments having a structure corresponding toat least one of a urethane reaction product and a urea reaction productof at least one monoisocyanate monomer. In a further refinement, thefourth backbone segments can be present in an amount ranging from 0.01wt. % to 4 wt. % relative to the thermoset polymer.

In a refinement, the composition further comprises one or more additivesselected from the group consisting of nanoclay, graphene oxide,graphene, silicon dioxide (silica), aluminum oxide, cellulosenanocrystals, carbon nanotubes, titanium dioxide (titania), diatomaceousearth, biocides, pigments, dyes, thermoplastics, and combinationsthereof.

In a refinement, the composition has a water contact angle in a rangefrom 90° to 120°. In another refinement, the composition has an oilcontact angle in a range from 0° or 1° to 65°. In another refinement,the composition has a water sliding angle in a range from 0° or 1° to30° for a 75 μl droplet. In another refinement, the composition has anoil sliding angle in a range from 0° or 1° to 20° for a 10 μl or 25 μldroplet. In the case of compositions further including one or morenanofillers (e.g., nanoclay, graphene oxide, graphene, silicon dioxide(silica), aluminum oxide, cellulose nanocrystals, carbon nanotubes,titanium dioxide), the contact angles suitably can range from 100° to150° for water, and from 20° to 120° for oil. Similarly, the slidingangles for water on the surface of nanofiller-containing compositionscan range from 0° or 1° to 20° for a 25 μl droplet.

In a refinement, the composition has a composite structure comprising: asolid matrix comprising the first backbone segments and the thirdbackbone segments; and liquid nanodomains comprising the second backbonesegments, the liquid nanodomains being distributed throughout the solidmatrix and having a size of 80 nm or less.

In another aspect, the disclosure relates to a coated articlecomprising: (a) a substrate; and (b) a thermoset omniphobic compositionaccording to any of the variously disclosed embodiments, coated on asurface of the substrate.

Various refinements of the disclosed coated article are possible.

In a refinement, the substrate is selected from the group of metal,plastics, a different thermoset material, glass, wood, fabric (ortextile), and ceramics.

In a refinement, the thermoset omniphobic composition has a thicknessranging from 0.01 μm to 500 μm.

In a refinement, the thermoset omniphobic composition coating isscratch-resistant, ink-resistant, dirt-repellent, and optically clear.For example, the coating can have a scratch resistance value of 7-10,8-10, 9-10, or 10 as evaluated by the “Scratch Resistance” methoddescribed below. Similarly, the coating can have an ink resistance valueof 7-10, 8-10, 9-10, or 10 as evaluated by the “Permanent InkResistance” method described below.

In another aspect, the disclosure relates to a method for forming athermoset omniphobic composition, the method comprising: (a) reacting atleast one polyisocyanate, at least one amine-functional hydrophobicpolymer having a glass transition temperature (T_(g)) of 50° C. or less,and at least one polyol to form a partially crosslinked reactionproduct; and (b) curing the partially crosslinked reaction product toform the thermoset omniphobic composition (e.g., as described aboveand/or according to any of the variously disclosed embodiments).

Various refinements of the disclosed method are possible.

In a refinement, the method comprises reacting the at least onepolyisocyanate, the at least one amine-functional hydrophobic polymer,and the at least one polyol to form the partially crosslinked reactionproduct (i) at temperature from 20° C. or 40° C. to 80° C. or 100° C.and (ii) for a time from 5 min to 300 min. In a further refinement, themethod comprises curing the partially crosslinked reaction product toform the thermoset omniphobic composition (i) at temperature from 20° C.to 30° C. and (ii) for a time from 4 hr to 240 hr. In a furtherrefinement, the method comprises reacting the at least onepolyisocyanate, the at least one amine-functional hydrophobic polymer,and the at least one polyol to form the partially crosslinked reactionproduct in a reaction solvent comprising one or more of a ketone (ormixtures of ketones), an ester (or mixtures of esters), dimethylformamide, and dimethyl carbonate.

In a refinement, the method comprises mixing while reacting the at leastone polyisocyanate, the at least one amine-functional hydrophobicpolymer, and the at least one polyol to form the partially crosslinkedreaction product

In a refinement, reacting the at least one polyisocyanate, the at leastone amine-functional hydrophobic polymer, and the at least one polyol toform the partially crosslinked reaction product comprises: reacting theat least one polyisocyanate and the at least one amine-functionalhydrophobic polymer in the absence of the at least one polyol to form aninitial reaction product; and reacting the at least one polyol with theinitial reaction product to form partially crosslinked reaction product.

In a refinement, curing the partially crosslinked reaction product toform the thermoset omniphobic composition comprises: adding a castingsolvent to the partially crosslinked reaction product; applying thecasting solvent and the partially crosslinked reaction product to asubstrate; drying the substrate to remove the casting solvent, therebyforming a coating of the partially crosslinked reaction product on thesubstrate; and curing the coating of the partially crosslinked reactionproduct on the substrate, thereby forming a coating of the thermosetomniphobic composition on the substrate. In a further refinement, themethod comprises performing one or more of spraying, casting, rolling,and dipping to apply the casting solvent and the partially crosslinkedreaction product to the substrate.

In a refinement, curing the partially crosslinked reaction product toform the thermoset omniphobic composition comprises: applying thepartially crosslinked reaction product to a substrate; drying thesubstrate, thereby forming a coating of the partially crosslinkedreaction product on the substrate; and curing the coating of thepartially crosslinked reaction product on the substrate, thereby forminga coating of the thermoset omniphobic composition on the substrate. In afurther refinement, the method comprises performing one or more ofspraying, casting, rolling, and dipping to apply the partiallycrosslinked reaction product to the substrate. In another refinement,the method comprises reacting the at least one polyisocyanate, the atleast one amine-functional hydrophobic polymer, and the at least onepolyol to form the partially crosslinked reaction product in a reactionsolvent; applying the partially crosslinked reaction product in thereaction solvent to a substrate; and drying the substrate, therebyremoving at least some of the reaction solvent and forming a coating ofthe partially crosslinked reaction product on the substrate.

While the disclosed methods and compositions are susceptible ofembodiments in various forms, specific embodiments of the disclosure areillustrated (and will hereafter be described) with the understandingthat the disclosure is intended to be illustrative, and is not intendedto limit the claims to the specific embodiments described andillustrated herein.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the disclosure, reference should bemade to the following detailed description and accompanying drawingswherein:

FIG. 1 is a diagram illustrating measurement of a contact angle for aliquid droplet on a surface.

FIG. 2 is a diagram illustrating how contact angles for a given liquiddroplet on a surface can vary as a function of surface topology (e.g.,flat or smooth surface vs. textured surfaces).

FIG. 3 illustrates a thermoset omniphobic composition according to thedisclosure.

FIG. 4 illustrates a coated article according to the disclosure in whichthe thermoset omniphobic composition has a composite structure.

FIG. 5 illustrates a coated article according to the disclosure in whichthe thermoset omniphobic composition has a homogeneous structure.

DETAILED DESCRIPTION

The disclosure relates to a thermoset omniphobic composition whichincludes a thermoset polymer with first, second, and third backbonesegments, urethane groups linking the first and third backbone segments,and urea groups linking the first and second backbone segments. Thefirst, second, and third backbone segments generally correspond tourethane or urea reaction products of polyisocyanate(s),amine-functional hydrophobic polymer(s), and polyol(s), respectively.The thermoset omniphobic composition has favorable omniphobicproperties, for example as characterized by water and/or oil contactand/or sliding angles. The thermoset omniphobic composition can be usedas a coating on any of a variety of substrates to provide omniphobicproperties to a surface of the substrate. Such omniphobic coatings canbe scratch resistant, ink/paint resistant (e.g., as an anti-graffiticoating), and/or optically clear.

The disclosed composition includes a polymer which can be used as acoating with the ability to bind to metal, glass, wood, fabrics, andceramics with relative ease, in particular due to the strong adhesiveproperties of its urethane group constituents. The polymer coating hasan omniphobic quality, repelling water, oils, inks, and spray paints,thus allowing for a coating that not only has typical hydrophobic andoleophobic properties, but also protects a surface from pen inks andvarious paints. The final polymer product is optically clear (even forrelatively thick coatings), making it an ideal choice for coatingcomputer and phone screens as well as windows. The polymer can bemanufactured without fluorine as a component and/or as a one-potreaction process, thus reducing the overall cost when compared toproducts currently manufactured. Coatings formed from the polymercomposition are durable due to the final crosslinked thermoset matrix.The composition can be used in water-repellent, oil-repellent,anti-fingerprint, anti-smudge, and/or anti-graffiti coatings or paints.

Omniphobic Composition

FIG. 3 illustrates a thermoset omniphobic composition according to thedisclosure. FIG. 3 qualitatively illustrates various backbone segments(B) and linking groups (L) in a crosslinked thermoset polymer 100. Thethermoset polymer 100 includes a crosslinked backbone B, which in turnincludes (i) first backbone segments B1, (ii) second backbone segmentsB2, (iii) third backbone segments B3, (iv) urethane (or carbamate)linking groups L1 linking first backbone segments and third backbonesegments, and (v) urea linking groups L2 linking first backbone segmentsand second backbone segments. As described in more detail below, thefirst backbone segments B1 generally result from a polyisocyanate (e.g.,monomer, oligomer, or polymer), the second backbone segments B2generally result from a polysiloxane or other hydrophobic polymer, andthe third backbone segments B3 generally result from a polyol (e.g.,monomer, oligomer, or polymer). The urethane (or carbamate) linkinggroups L1 can be represented by the general structure —NR₁—C(═O)O—,where R₁ can be H or a C₁-C₁₂ linear, branched, or cyclic substituted orunsubstituted hydrocarbon group, such as an aliphatic (e.g., alkyl,alkenyl) group or an aromatic group, or a combination of different R₁groups (such as when multiple different reactive components are used).The urea linking groups L2 can be represented by the general structure—NR₂—C(═O)—NR₃—, where R₂ and R₃ independently can be H or a C₁-C₁₂linear, branched, or cyclic substituted or unsubstituted hydrocarbongroup, such as an aliphatic (e.g., alkyl, alkenyl) group or an aromaticgroup, or a combination of different R₂ and/or R₃ groups (such as whenmultiple different reactive components are used).

The first backbone segments B1 generally have a structure correspondingto at least one of a urethane reaction product and a urea reactionproduct from at least one polyisocyanate (e.g., diisocyanate,triisocyanate, or higher degree of isocyanate functionality) with apolyol (urethane) or an amine-functional hydrophobic polymer (urea). Thefirst backbone segments B1 can result from a single polyisocyanate(e.g., a diisocyanate, a triisocyanate) species or a blend of two ormore different polyisocyanate species with the same or different degreeof isocyanate functionality.

The second backbone segments B2 have a structure corresponding to a ureareaction product from at least one amine-functional hydrophobic polymerhaving a glass transition temperature (T_(g)) of 50° C. or less (e.g.,monoamine-functional, diamine-functional, or higher degree of aminefunctionality) and a polyisocyanate. In various embodiments, theamine-functional hydrophobic polymer has a glass transition temperaturein a range from −150° C. to 50° C. (e.g., at least −150° C., −120° C.,−100° C., or −50° C. and/or up to −10° C., 0° C., 10° C., 20° C., 30°C., 40° C., or 50° C.). The amine-functional hydrophobic polymer can beeither in a liquid or a rubbery state at common use temperatures of thefinal coating, for example in a range from 10° C. to 40° C. or 20° C. to30° C. In various embodiments, the amine-functional hydrophobic polymeris a liquid at a temperature in a range from 10° C. to 40° C. (e.g.,from 20° C. to 30° C., or about room temperature, such as where theamine-functional hydrophobic polymer has a melting temperature (T_(m))below 10° C. or 20° C.). The amine groups can be terminal and/or pendantfrom the hydrophobic polymer. In an embodiment, the amine groups areterminal groups on a hydrophobic polymer (e.g., linear hydrophobicpolymer with one or two terminal amine groups). The second backbonesegments B2 can result from a single amine-functional hydrophobicpolymer species or a blend of two or more different amine-functionalhydrophobic polymer species with the same or different degree of aminefunctionality. The amine-functional hydrophobic polymers can generallyinclude one or more of amine-functional polysiloxanes, amine-functionalpolyperfluoroethers, amine-functional polybutadienes, amine-functionalpoly(ethylene glycol) methyl ether (“PEO”), amine-functionalpolyisobutylene (“PIB”), amine-functional branched polyolefins,amine-functional polyacrylates and polymethacrylates (e.g., alsoincluding C₂-C₁₆ pendant alkyl groups), and any other hydrophobicpolymer with a glass transition temperature of 50° C. or less. In anembodiment, the amine-functional hydrophobic polymers, the secondbackbone segments B2, and/or the corresponding omniphobic compositioncan be free from fluorine or fluorinated components (e.g., not usingamine-functional polyperfluoroethers or other fluorine-containingcomponents during synthesis).

The third backbone segments B3 have a structure corresponding to aurethane reaction product from at least one polyol (e.g., diol, triol,or higher degree of hydroxyl functionality) and a polyisocyanate. Thethird backbone segments B3 can result from a single polyol species or ablend of two or more different polyol species with the same or differentdegree of hydroxyl functionality.

The urethane (or carbamate) groups L1 have a structure corresponding toa urethane reaction product of the polyisocyanate and the polyol, andthe urea groups L2 have a structure corresponding to a urea reactionproduct of the polyisocyanate and the amine-functional hydrophobicpolymer.

The polyisocyanate is not particularly limited and generally can includeany aromatic, alicyclic, and/or aliphatic isocyanates having at leasttwo reactive isocyanate groups (—NCO). Suitable polyisocyanates containon average 2-4 isocyanate groups. In some embodiments, thepolyisocyanate includes a diisocyanate. In some embodiments, thepolyisocyanate includes triisocyanate. Suitable diisocyanates can havethe general structure (O═C═N)—R—(N═C═O), where R can include aromatic,alicyclic, and/or aliphatic groups, for example having at least 2, 4, 6,8, 10 or 12 and/or up to 8, 12, 16, or 20 carbon atoms. Examples ofspecific polyisocyanates include 1,5-naphthylene diisocyanate,4,4′-diphenylmethane diisocyanate (MDI), hydrogenated MDI, xylenediisocyanate (XDI), tetramethylxylol diisocyanate (TMXDI),4,4′-diphenyl-dimethylmethane diisocyanate, di- andtetraalkyl-diphenylmethane diisocyanate, 4,4′-dibenzyl diiso-cyanate,1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, one or moreisomers of tolylene diisocyanate (TDI, such as toluene2,4-diisocyanate), 1-methyl-2,4-diiso-cyanatocyclohexane,1,6-diisocyanato-2,2,4-trimethyl-hexane,1,6-diisocyanato-2,4,4-trimethylhexane,1-iso-cyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinatedand brominated diisocyanates, phosphorus-containing diisocyanates,4,4′-diisocyanatophenyl-perfluoroethane, tetramethoxybutane1,4-diisocyanate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate (orhexamethylene diisocyanate; HDI), HDI dimer (HDID), HDI trimer (HDIT),HDI biuret, dicyclohexylmethane diisocyanate, cyclohexane1,4-diisocyanate, ethylene diisocyanate, phthalic acidbisisocyanatoethyl ester, 1-chloromethylphenyl 2,4-diisocyanate,1-bromomethylphenyl 2,6-diisocyanate, 3,3-bischloromethyl ether4,4′-diphenyldiisocyanate, trimethylhexamethylene diisocyanate,1,4-diisocyanato-butane, 1,2-diisocyanatododecane, and combinationsthereof. The polyisocyanate can be biobased or made of syntheticfeedstock. Examples of suitable biobased polyisocyanates includepentamethylene diisocyanate trimer, and polyisocyanates formed from basecompounds to which isocyanate groups are attached (e.g., via suitablederivatization techniques), including isocyanate-terminated poly(lactidacid) having two or more isocyanate groups, isocyanate-terminatedpoly(hydroxyalkanaotes) having two or more isocyanate groups,isocyanate-terminated biobased polyesters having two or more isocyanategroups.

The amine-functional hydrophobic polymer is not particularly limited andgenerally can include any hydrophobic polymer with glass transitiontemperature of 50° C. or less, such as in a range from −150° C. to 50°C. Examples of general classes of amine-functional hydrophobic polymersinclude amine-functional polysiloxanes, amine-functionalpolyperfluoroethers, amine-functional polybutadienes, amine-functionalpolyolefins (e.g., polyethylene, polypropylene, polybutylene), andcombinations or mixtures thereof. The amine groups in theamine-functional hydrophobic polymers can include one or both of aprimary amine and a secondary amine (e.g., R¹NH₂ and R¹R²NH,respectively, where R¹ and R² can be the same or different groups otherthan hydrogen, for example hydrocarbon groups). The amine-functionalpolyperfluoroether (e.g., amine-functional polyperfluoropolyethers) caninclude mono-, di-, or higher amine functional polyperfluoroethers, or ablend of thereof, such as a blend of mono- and diamine-functionalpolyperfluorothers. The amine-functional polybutadiene can includemono-, di-, or higher amine functional polybutadienes, or a blend ofthereof, such as a blend mono- and diamine-functional polybutadienes.Many suitable amine-functional hydrophobic polymers are commerciallyavailable (e.g., amine-functional PDMS with a variety of availabledegrees of functionality and molecular weights). Hydrophobic polymersthat are not commercially available in their amine-functional form canbe amine functionalized using conventional chemical synthesistechniques, for example including but not limited to hydroamination,thiol-ene Michael reaction of amine-carrying thiols, Mitsunobu reaction,and reductive amination.

The amine-functional polysiloxane is not particularly limited andgenerally can include any polysiloxane having mono-, di-, or higheramine functionality. In some embodiments, the amine-functionalpolysiloxane includes a monoamine-functional polysiloxane. In someembodiments, the amine-functional polysiloxane includes adiamine-functional polysiloxane. The polysiloxane can be apolydialklylsiloxane having —Si(R₁R₂)—O— repeat units, where R₁ and R₂independently can be C₁-C₁₂ linear or branched alkyl groups, C₄-C₁₂cycloalkyl groups, unsubstituted aromatic groups, or substitutedaromatic groups, in particular where R₁ and R₂ are methyl groups for apolydimethylsiloxane (PDMS). The amine groups are suitably terminalamine groups, for example in a polydialklylsiloxane represented byNH₂—R₃—[Si(R₁R₂)—O]x-R₃—NH₂ for a diamine or NH₂—R₃—[Si(R₁R₂)—O]X—R₃ fora monoamine, where R₃ independently can be H (when a terminal group) orC₁-C₁₂ linear or branched alkyl (when a terminal group or a linker for aterminal amine). The amine groups additionally can be pendant aminegroups, for example in a polydialklylsiloxane represented byR₃—[Si(R₁R₂)—O]X—[Si(R_(1′)R_(2′))—O]_(x)—R₃, where R_(1′) and R_(2′)independently can be the same as R₁ and R₂, but at least one or both ofR_(1′) and R_(2′) independently is a C₁-C₁₂ linear or branched alkyllinker group with a terminal amine group (e.g., —NH₂). Some examples ofpolyslioxanes with amine group(s) include amine-bearingpolydimethylsiloxane, amine-bearing polymethylphenylsiloxane, andamine-bearing polydiphenylsiloxane.

Some examples of polyperfluoropolyethers with amine group(s) includeamine-bearing poly(n-hexafluoropropylene oxide) (—(CF₂CF₂CF₂O)n-)NH₂)and amine-bearing poly(hexafluoroisopropylene oxide) (—(CF(CF₃)CF₂O)nNH₂or PFPO—NH₂). Some examples of amine-bearing atactic polyolefins includeamine-bearing poly(1-butene), branched polyethylene, poly(cis-isoprene),poly(trans-isoprene), and poly (1-octene). Some examples ofamine-bearing polyacrylates include poly(3-amino propyl acrylate).Similarly, mono-functional amine-bearing polymers include monoaminepolyisobutylene (PIB—NH₂), monoamine polypolyethylene glycol (PEG-NH₂),monoamine poly(1-butene) (PB—NH₂, cis and trans) can also be used as thelow-glass transition temperature (T_(g) less than 50° C.) polymers,either alone or in combination with other amine-functional hydrophobicpolymers.

The amine-functional hydrophobic polymer can have any suitable molecularweight in view of desired glass transition temperature, for examplehaving a molecular weight ranging from 300 to 50,000 g/mol. In variousembodiment, the molecular weight can be at least 300, 800, 1000, 1500,or 2000 and/or up to 1000, 2000, 3000, 5000, or 50,000 g/mol. Themolecular weight can be expressed as a number-average or weight-averagevalue in the units of gram/mole (g/mol). Some embodiments can include ablend of two or more amine-functional hydrophobic polymers withdifferent average molecular weights, such as one with 300-1500 g/mol andanother with 1500-50,000 g/mol with a higher average molecular weightthan the first. Blends of amine-functional hydrophobic polymers (e.g.,differing in molecular weight and/or in degree of functionality) canimprove the combination of water- and oil-repellency properties of thefinal composition. For example, a monoamine-functional polysiloxane canprovide better water and oil repellency than a diamine-functionalpolysiloxane. Low MW amine-functional polysiloxanes (e.g., PDMS, such ashaving a MW range of about 800-1200 g/mol or an average MW of about 1000g/mol) can provide an improved water repellency, while Higher MWamine-functional polysiloxanes (e.g., PDMS, such as about 2000 g/mol orabove for an average or range of MW) can provide an improved oilrepellency.

The polyol is not particularly limited and generally can include anyaromatic, alicyclic, and/or aliphatic polyols with at least two reactivehydroxyl/alcohol groups (—OH). Suitable polyol monomers contain onaverage 2-4 hydroxyl groups on aromatic, alicyclic, and/or aliphaticgroups, for example having at least 4, 6, 8, 10 or 12 and/or up to 8,12, 16, or 20 carbon atoms. In some embodiments, the polyol is a diol.In some embodiments, the polyol is a triol. Examples of specific polyolsinclude one or more of polyether polyols (e.g., polypropyleneoxide-based triols such as commercially available MULTRANOL 4011 with aMW of about 300), triethanolamine, hydroxlated (meth)acrylate oligomers(e.g., 2-hydroxylethyl methacrylate or 2-hydroxyethyl acrylate),glycerol, ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, dipropylene glycol, tripropyleneglycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerol,trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, (meth)acrylicpolyols (e.g., having random, block, and/or alternating hydroxylfunctionalities along with other (meth)acrylic moieties), polyesterpolyols, and/or polyurethane polyols. The polyol can be biobased or madeof synthetic feedstock. Examples of suitable biobased polyols includeisosorbide, poly(lactic acid) having two or more hydroxyl groups,poly(hydroxyalkanaotes) having two or more hydroxyl groups, and biobasedpoly(esters) having two or more hydroxyl groups (e.g., as terminalgroups).

In some embodiments, at least one of the polyisocyanate and the polyolis a tri- or higher functional isocyanate or alcohol/hydroxy compound,respectively, to promote crosslinking of the backbone segments in thefinal thermoset polymer. Alternatively or additionally, in someembodiments, the amine-functional hydrophobic polymer is a tri- orhigher amine-functional compound (e.g., tri-functional amine PDMS) sothat the hydrophobic polymer can serve as a crosslinker, either alone orin combination with polyisocyanate and/or polyol crosslinkers.

The first, second, and third backbone segments can be incorporated intothe thermoset polymer in a variety of relative weight amounts. In anembodiment, the first backbone segments are present in an amount rangingfrom 10 wt. % to 90 wt. % relative to the thermoset polymer (e.g., atleast 10, 15, or 20 wt. % and/or up to 30, 40, 50, 60, 70, 80, or 90 wt.%; such as 30 wt. % to 70 wt. %), which amounts can equivalentlycorrespond to the polyisocyanate(s), for example as added to a reactionmixture and relative to all monomeric, oligomeric, and polymericreaction components added thereto. In an embodiment, the second backbonesegments are present in an amount ranging from 0.01 wt. % to 20 wt. %relative to the thermoset polymer (e.g., at least 0.01, 0.1, 0.2, 0.5,1, 2, 3, or 5 wt. % and/or up to 3, 5, 8, 10, 15 or 20 wt. %; such as0.2 wt. % to 8 wt. % or 1 wt. % to 5 wt. %), which amounts canequivalently correspond to the amine-functional hydrophobic polymer(s),for example as added to a reaction mixture and relative to allmonomeric, oligomeric, and polymeric reaction components added thereto.In an embodiment, the third backbone segments are present in an amountranging from 10 wt. % to 90 wt. % relative to the thermoset polymer(e.g., at least 10, 20, 30, 40, or 50 wt. % and/or up to 70, 80, or 90wt. %, such as 30 wt. % to 70 wt. %), which amounts can equivalentlycorrespond to the polyol monomer(s), for example as added to a reactionmixture and relative to all monomeric, oligomeric, and polymericreaction components added thereto.

Similarly, the first, second, and third backbone segments can beincorporated into the thermoset polymer in a variety of relative molaramounts based on the corresponding reactive functional groups of theircorresponding monomeric, oligomeric, and polymeric reaction components.Suitably, approximately a 1:1 molar ratio of combined hydroxy and aminofunctional groups (from the polyol(s) and amine-functional hydrophobicpolymer(s), respectively) relative to isocyanate groups (from thepolyisocyanate(s)) is used when combining reactive components to makethe omniphobic composition. In most cases, isocyanate groups are addedin a slight molar excess. Final molar ratios of (i) isocyanate groups to(ii) hydroxy groups and amine-functional groups combined are typicallybetween 1:1 to 1.6:1, for example at least 1:1, 1.1:1, or 1.2:1 and/orup to 1.4:1, 1.5:1, or 1.6:1.

In an embodiment, the thermoset polymer crosslinked backbone can includefurther types of backbone segments. For example, the backbone caninclude fourth backbone segments which have a structure corresponding toat least one of a urethane reaction product and a urea reaction productof at least one monoisocyanate (e.g., when a monoisocyanate is includedwith the polyisocyanate and the other reaction components forming theomniphobic composition). The monoisocyanate can be a reactive monomerwith only one isocyanate reactive group, which can be used as a means tocontrol crosslinking degree as well as to incorporate hydrophobic orother functional groups at an external or boundary portion of thethermoset polymer. Examples of monoisocyanates include R—(N═C═O), whereR can include aromatic, alicyclic, and/or aliphatic groups, for examplehaving at least 2, 4, 6, 8, 10 or 12 and/or up to 8, 12, 16, or 20carbon atoms. The fourth backbone segments can be present in an amountranging from 0.01 wt. % to 4 wt. % relative to the thermoset polymer(e.g., at least 0.01, 0.1, 0.2, or 0.5 wt. % and/or up to 1, 2, or 4 wt.%), which amounts can equivalently correspond to the monoisocyanatemonomer, for example as added to a reaction mixture and relative to allmonomeric, oligomeric, and polymeric reaction components added thereto.

In an embodiment, the omniphobic composition can include any suitableorganic or inorganic filler or additive, which can be included toimprove one or more of mechanical properties, optical properties,electrical properties, and omniphobic properties of the finalcomposition. Examples of suitable fillers or additives include nanoclay,graphene oxide, graphene, silicon dioxide (silica), aluminum oxide,diatomaceous earth, cellulose nanocrystals, carbon nanotubes, titaniumdioxide (titania), and combinations or mixtures thereof. In addition,the fillers can include biocides, pigments, dyes, a thermoplasticmaterial, or a combination thereof. The fillers can be added in therange from 0.01 wt. % to 10 wt. %, for example in range from 1 wt. % to5 wt. %. The presence of organic or inorganic fillers in the omniphobiccomposition can affect the clarity of the resulting composition, inwhich case the amount and size of the fillers can be selected in view ofthe desired clarity properties of the composition as well as themechanical, electrical, omniphobic or other functional properties of thefinal composition.

The omniphobic properties of the thermoset composition (e.g., for thecured composition) can be characterized in terms of one or more contactangles and/or sliding angles for water and/or oil droplets (e.g.,vegetable oil and/or hexadecane) on the thermoset composition (e.g., asa coating on a substrate). The following ranges are representative ofcompositions according to the disclosure which display favorableomniphobic properties. In an embodiment, the composition has a watercontact angle in a range from 90° to 120° (e.g., at least 90°, 95°,100°, or 105° and/or up to 110°, 115°, or 120°; such as for the curedcomposition as a coating). In some cases, the water contact angle can beup to about 125° for non-smooth or rough surfaces. In an embodiment, thecomposition has an oil contact angle in a range from 0° or 1° to 65°(e.g., at least 1°, 10°, 20°, or 30° and/or up to 40°, 50°, 60°, or 65°;such as for the cured composition as a coating). In an embodiment, thecomposition has a water sliding angle in a range from 0° or 1° to 30°for a 75 μl droplet (e.g., at least 1°, 2°, 4°, 6°, or 8° and/or up to10°, 15°, 20°, or 30°; such as for the cured composition as a coating).In an embodiment, the composition has an oil sliding angle in a rangefrom 0° or 1° to 20° for a 10 μl or 25 μl droplet (e.g., at least 1°,2°, 4°, 6°, or 8° and/or up to 10°, 12°, 15°, or 20°; such as for thecured composition as a coating). The contact angles for the omniphobiccoatings can be higher when nanofillers (e.g., clay, silica, etc.) areincluded in the composition as compared to corresponding compositionswithout any nanofillers.

In an embodiment, the thermoset omniphobic composition has a compositestructure as illustrated in FIG. 4 . The composite structure can includea solid matrix formed primarily from the first backbone segments and thethird backbone segments linked together (e.g., with or without somesecond backbone segments incorporated therein). The composite structurecan further include nanodomains distributed throughout the solid matrix.The nanodomains are formed primarily from the second backbone segments(e.g., with or without minor amounts of first and/or third backbonesegments incorporated therein), and generally have a size of 80 nm orless, more preferably 40 nm or less. The nanodomains can be liquidnanodomains or rubbery nanodomains, depending on the usage temperatureof the omniphobic composition relative to the glass transition andmelting temperatures of the amine-functional hydrophobic polymerprecursor to the second backbone segments. For example, the nanodomainscan have a size or diameter of at least 0.1, 1, 10, 15 or 20 nm and/orup to 30, 40, 50, or 80 nm; for example 1 nm to 40 nm or 1 nm to 80 nm.The ranges can represent a distribution of sizes for the nanodomainsand/or a range for an average nanodomain size (e.g., weight-, number-,or volume-average size). In a lower limit as the size of the nanodomainsapproaches zero, the composition approaches a homogeneous structure as ahomogeneous thermoset solid with the first, second, and third backbonesegments being generally evenly distributed throughout the omniphobiccomposition as illustrated in FIG. 5 .

Coated Article

FIGS. 4 and 5 illustrate an aspect of the disclosure in which a coatedarticle 300 (e.g., desirably having omniphobic properties on at leastone surface thereof) includes a substrate 200 and the thermosetomniphobic composition 100 coated on a surface 202 of the substrate 200.The composition 100 can be in the form of a coating or film on anexternal, environment-facing surface 202 of the substrate 200 (e.g.,where the surface 202 would otherwise be exposed to the externalenvironment in the absence of the composition 100). In this case, thethermoset omniphobic composition 100 provides omniphobic protection tothe underlying substrate 200.

The substrate 200 is not particularly limited, and generally can beformed from any material desired for protection with an omniphobiccoating, in particular given the good, broad adhesive capabilities ofthe thermoset omniphobic composition 100. For example, the substrate canbe a metal, plastic, a different thermoset material (e.g., a primermaterial; material other than the other than thermoset omniphobiccomposition), glass, wood, fabric (or textile), or ceramic material.Examples of specific metals include steel, aluminum, copper, etc.Examples of specific plastics include polyvinyl alcohol (PVOH), ethylenevinyl alcohol (EVOH), polyethylene terephthalate (PET), polypropylene(PP), polyethylene (PE), polylactic acid (PLA), starch, chitosan, etc.In an embodiment, the substrate can be in the form of athree-dimensionally printed substrate, whether formed from apolymeric/plastic material or otherwise. Suitable wood materials can beany type of wood commonly used in home, office, and outdoor settings.Suitable glass materials can be those used for building windows,automobile windows, etc. In some embodiments, the substrate 200 is a toplayer of a coating or series of coatings on a different underlyingsubstrate. For example, the coated article can include a substrate 200material as generally disclosed herein, one or more intermediatecoatings on the substrate 200 (e.g., an epoxy coating, an acryliccoating, another primer coating, etc.), and the thermoset omniphobiccomposition 100 on the one or more intermediate coatings as the final,external coating on the coated article 300.

The thermoset omniphobic composition 100 can have any desired thicknesson the substrate 200. In common applications, the composition 100 has athickness ranging from 0.010 μm to 500 μm, for example at least 0.01,10, 20, 50, or 100 μm and/or up to 200, 500 μm. Typical cast coatingscan have thicknesses of 10 μm to 100 μm. Typical spin coatings can havethicknesses of 0.05 μm or 0.10 μm to 0.20 μm or 0.50 μm. Multiplecoating layers can be applied to substrate 200 to form even thickerlayers of the composition 100 (e.g., above 500 μm or otherwise) ifdesired.

Method of Making Composition and Coated Article

The thermoset omniphobic composition according to the disclosuregenerally can be formed by first reacting the polyisocyanate(s), theamine-functional hydrophobic polymer(s), and the polyol(s) to form apartially crosslinked (e.g., not fully crosslinked) reaction product,and then curing the partially crosslinked reaction product to form thethermoset omniphobic composition (e.g., after application a substrate toprovide an omniphobic coating thereon). The partially crosslinkedreaction product contains at least some unreacted isocyanate, hydroxy,and/or amine groups for eventual further reaction during curing/fullcrosslinking. In some embodiments, the partially crosslinked reactionproduct contain at least some unreacted isocyanate and hydroxy groups,but is free or substantially free of unreacted amine groups (e.g., whereall or substantially all of the amine groups in the amine-functionalhydrophobic polymer have reacted with an isocyanate group, but thepolyisocyanates still have at least some free some unreacted isocyanategroups remaining). The initial, partial crosslinking reaction can beperformed in a suitable reaction solvent or medium, for example anaprotic organic solvent such as acetone, tetrahydrofuran, 2-butanone,other ketones (e.g., methyl n-propyl ketone, methyl isobutyl ketone,methyl ethyl ketone, ethyl n-amyl ketone), esters (e.g., C₁-C₄ alkylesters of C₁-C₄ carboxylic acids, such as methyl, ethyl, n-propyl, butylesters of acetic acid such as n-butyl acetate, etc., n-butyl propionate,ethyl 3-ethoxy propionate), dimethylformamide, dimethyl carbonate, etc.In some cases, a mixture of two or more solvents can be used for theinitial, partial crosslinking reaction. In some embodiments, a reactioncatalyst is added to catalyze the reaction between the polyisocyanateand the polyol. Various commercial and laboratory-synthesized catalystscan be used, for example including, but not limited to, complexes and/orsalts of tin (e.g., tin(II) 2-ethylhexanoate) or iron, and tertiaryamines (e.g., triethylamine), 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU)and 1,4-Diazabicyclo[2.2.2]octane (DABCO). Curing can be performed byheating (e.g., in an oven, with exposure to a heat lamp, etc.) at atemperature from 80° C. or 100° C. to 140° C. or 180° C. and/or for atime from 1 hr to 24 hr. Lower heating temperature or ambienttemperature curing also possible, such as room temperature curing (e.g.,20° C. to 30° C.) for 4 hr-240 hr or 5-10 days (e.g., at least 4, 8, 12,16, or 24 hr and/or up to 12, 16, 24, 48, 72, 96, 120, or 240 hr), lowerheating (e.g., 30° C. or 40° C. to 60° C. for 4 hr-96 hr or 2-4 days or60° C. to 80° C. for 1 hr-72 hr or 1-3 days).

Reaction to form the partially crosslinked reaction product generallycan be performed at any suitable reaction temperature(s) and time(s),which can be selected such that there is sufficient time to partially(but not completely) crosslink/cure the components of the reactionmixture, thus leaving some reactive functional groups for eventual fullcuring/crosslinking in the final thermoset composition. In anembodiment, reaction to form the partially crosslinked reaction productis performed (i) at temperature from 20° C. or 40° C. to 80° C. or 100°C. and (ii) for a time from 5 min to 300 min. Thus, reaction can beperformed with or without heating the reaction mixture. Room-temperature(e.g., 20° C. to 30° C.) reactions are possible with longer reactiontimes and/or the addition of a catalyst. The initial reaction betweenthe polyisocyanate and the hydrophobic polymer is generally very fastand need not be heated for suitable reaction times. Subsequent reactionbetween the polyisocyanate and the polyol is slower and preferablyinvolves heating and/or the use of a catalyst.

In an embodiment, reaction to form the partially crosslinked reactionproduct includes stirring or otherwise mixing the reaction components toimprove reactant homogeneity and that of the eventual product. Mixing orstirring during the reaction between the polyisocyanate and thehydrophobic polymer (e.g., whether the two are reacted/combinedseparately from or together with the polyol) is particularly desirablebecause the isocyanate/amine reaction is generally very fast, and mixingof the reaction mixture is desirable to help form a distributedpartially cured reaction product in which most polyisocyanate moleculeshave at least one free isocyanate functional group for eventual reactionwith a polyol molecule. Put another way, stirring/mixing helps to avoida situation in which some polyisocyanate molecules have all of theirisocyanate groups reacted with amine groups from the amine-functionalhydrophobic polymer, which in turn prevents further reaction with apolyol molecule for incorporation into the crosslinked network of thethermoset polymer and can lead to opaque or hazy films (i.e., instead ofdesirably transparent films). Accordingly, mixing/stirring combined withappropriate selection of stoichiometric ratios between thepolyisocyanate, the amine-functional hydrophobic polymer, and the polyolhelps to ensure that most, if not all or substantially all,polyisocyanate molecules react with at least one polyol molecule (e.g.,having at least one urethane link).

In an embodiment, reaction to form the partially crosslinked reactionproduct includes first reacting the polyisocyanate and theamine-functional hydrophobic polymer (e.g., in the absence of thepolyol) to form an initial reaction product. Reaction to form theinitial reaction product is preferably performed with mixing or stirringas above to obtain a good distribution of unreacted polyisocyanatemolecules and/or partially amine-reacted polyisocyanate molecules withat least one isocyanate group available for further reaction. Theinitial reaction product suitably contains amine-reacted polyisocyanatemolecules as well as possibly one or both of unreacted polyisocyanatemolecules and unreacted amine-functional hydrophobic polymers. This stepcan be performed in a single reaction vessel prior to addition of the atleast one polyol, and is preferably performed in the absence of anyreactive hydroxyl-containing species, whether polyol or otherwise. Theinitial reaction product is then reacted with the polyol to formpartially crosslinked reaction product, for example by adding orotherwise combining the polyol with the initial reaction product betweenthe polyisocyanate and the amine-functional hydrophobic polymer (e.g.,in the same reaction vessel, and optionally with heating and/or furthercatalyst addition). This sequence of addition/reaction is preferable butrequired. Other sequences of addition or combination of all threereactive components at the same time are possible. In some cases, theresulting thermoset omniphobic composition might have relatively pooreroptical properties in terms of being partially opaque or not completelytransparent, but the composition generally has the same or comparableomniphobic properties with respect to contact and gliding angles, etc.

In an embodiment, curing the partially crosslinked reaction productincludes adding a casting solvent to the partially crosslinked reactionproduct. Suitably, the casting solvent is one that does not dissolve theamine-functional hydrophobic polymer, which is a suitable selectionwhether the final thermoset composition is desired to have aninhomogeneous composite-type structure with nanodomains as describedabove or a homogeneous structure Examples of suitable casting solventsinclude dimethyl carbonate, diethyl carbonate, dimethylformamide,dimethylacetamide, acetonitrile, etc. Further, it can be desirable toremove the reaction solvent used for form partially crosslinked reactionproduct, for example by heating and/or using a gas such as nitrogen(e.g., purging or bubbling the gas through the reaction mixture), sothat the partially crosslinked reaction product is in solution in thecasting solvent. The casting solvent and the partially crosslinkedreaction product are then applied to a substrate, which is subsequentlyair-dried to remove the casting solvent and form a coating of thepartially crosslinked reaction product on the substrate. The driedcoating is then cured as described above to form the thermosetomniphobic composition coating on the substrate. In most cases, thecured thermoset remains as a coating on the substrate to provideomniphobic properties to the substrate. In some embodiments, the curedthermoset can be deliberately peeled or otherwise removed from thesubstrate to provide a standalone composition in the form or a free filmor other coating. The coating can be applied using any suitable method,such as by casting, spraying, rolling and/or dipping.

In an embodiment, curing the partially crosslinked reaction productincludes applying the partially crosslinked reaction product to asubstrate (e.g., applied as dissolved/dispersed in its original reactionmedium or reaction solvent, without solvent exchange/addition with acasting solvent). The coated substrate is then dried (e.g., to removethe reaction solvent) to form a coating of the partially crosslinkedreaction product on the substrate. The dried coating is then cured asdescribed above to form the thermoset omniphobic composition coating onthe substrate.

EXAMPLES

The following examples illustrate the disclosed compositions andmethods, but are not intended to limit the scope of any claims thereto.In the following examples, thermoset omniphobic compositions generallyaccording to the disclosure are prepared and applied as a film orcoating on a test substrate such as glass. The applied films or coatingscan then be evaluated according to a variety of tests as described belowin order to characterized their relative degree of omniphobicity.

Contact Angle: Contact angles (see FIG. 1 ) are determined by applying aliquid droplet on a test coating surface that is stationary andhorizontal with respect to gravity. Any specified liquids can be used,but omniphobic coatings are generally characterized by determiningcontact angles for water droplets and separately for oil droplets (e.g.,a cooking or other common vegetable oil, hexadecane or other oily liquidhydrocarbon). The applied droplets have a volume of about 5 μl (e.g.,about 3 μl to 10 μl), although the measured contact angle is notparticularly sensitive to actual droplet volume in these ranges. Onceapplied to the test coating, the droplet can be visually interrogatedthrough any suitable means to determine the contact angle (e.g., usingconventional digital image photography and digital image analysis).Suitably, (cured) omniphobic composition coatings according to thedisclosure have a water contact angle in a range from 90° to 120° (e.g.,at least 90°, 95°, 100°, or 105° and/or up to 110°, 115°, or 120°).Suitably, (cured) omniphobic composition coatings according to thedisclosure have an oil contact angle in a range from 0° or 1° to 65°(e.g., at least 1°, 10°, 20°, or 30° and/or up to 40°, 50°, 60°, or65°).

Sliding Angle: Sliding angles are determined by applying a liquiddroplet on a test coating surface that is initially horizontal withrespect to gravity. The test coating surface is then gradually ramped ata controlled/known angle relative to the horizontal plane. Dropletswhich do not initially spread will remain stationary on the test surfaceuntil the test surface is ramped to a sufficiently high angle to causethe droplets to slide down the ramped test surface. The test surfaceangle at which sliding begins is the sliding angle of the test coating.Any specified liquids can be used, but omniphobic coatings are generallycharacterized by determining contact angles for water droplets andseparately for oil droplets (e.g., a cooking or other common vegetableoil, hexadecane or other oily liquid hydrocarbon). The applied dropletshave a specified volume, which is generally about 75 μl (e.g., about 50μl to 150 μl) for water and about 10 μl or 20 μl (e.g., about 5 μl to 40μl) for oil. Once applied to the test coating, the droplet can bevisually interrogated through any suitable means to determine thesliding angle (e.g., using conventional digital image photography anddigital image analysis). Suitably, (cured) omniphobic compositioncoatings according to the disclosure have a water sliding angle in arange from 0° or 1° to 30° (e.g., at least 1°, 2°, 4°, 6°, or 8° and/orup to 10°, 15°, 20°, or 30°). Suitably, (cured) omniphobic compositioncoatings according to the disclosure have an oil contact angle in arange from 0° or 1° to 20° (e.g., at least 1°, 2°, 4°, 6°, or 8° and/orup to 10°, 12°, 15°, or 20°).

Scratch Resistance: Scratch resistance is evaluated on a scale of 1(worst) to 10 (best) by attempting to scratch a test coating surfaceusing materials of various hardness, such as a human fingernail, thecorner/edge of a glass slide, a metal (e.g., stainless steel) knife,etc. The test surface is rated as “1” for a given scratching material ifthere is substantial damage or delamination of the test coating surfaceafter being scratched. The test surface is rated as “10” for a givenscratching material if there is no observable damage or marking on thetest coating surface after being scratched. These qualitative numberswere obtained based on the criteria including: 1) the depth of thescratch, 2) is scratch damaging the surface, and 3) whether the scratchbe felt if touched by hand.

Permanent Ink Resistance: Permanent ink resistance is evaluated on ascale of 1 (worst) to 10 (best) by applying an ink marking on a testcoating surface using a permanent ink marker (e.g., SHARPIE permanentink marker or equivalent) and then attempting to wipe off the markingusing a tissue (e.g., KIMWIPE laboratory cleaning tissue or equivalent).The test surface is rated as “1” if all of the ink marking remains onthe test coating surface after being wiped. The test surface is rated as“10” if all of the ink marking is removed from the test coating surfaceafter being wiped. These numbers give an estimation of theink-resistance, which are qualitatively assigned by taking two aspectsin consideration: 1) the amount of ink left behind after a single wipeof the sample, and 2) the ink left behind after multiple wipes of thesample.

Example 1—One-Pot Synthesis of Omniphobic Polyurethane

2.2 ml (2.3 g) of poly(hexamethylene diisocyanate) (DESMODUR N 100A;Bayer Chemical Company, primarily including (trifunctional)triisocyanate species) was taken in a 20 ml vial, and was diluted with2.0 mL tetrahydrofuran (THF). To this solution, 0.05 ml (0.049 g)bis-(3-aminopropyl)-terminated polydimethylsiloxane (denoted asNH₂—PDMS-NH₂ or PDMS-diamine; (M_(n)=2500 g/mol); Sigma-Aldrich) wasdiluted with 0.2 ml THE and was added slowly under stirring.Subsequently, 0.68 ml (0.69 g) of polyether polyol (MULTRANOL 4011; ˜306MW g/mol triol; Bayer Chemical Company) was added to the 20 ml vial. Thevial was then heated and stirred at 60° C. for 20 minutes. The vial wascooled to room temperature and then 6 ml dimethyl carbonate (DMC) wasadded to the vial. THE from the solution was removed by bubbling ofnitrogen gas (or under reduced pressure). After complete removal of THF,the remaining coating solution in DMC was cast on a 3 inch×1 inch microglass slide by placing them on a leveled surface. The cast film was airdried for 30 minutes before curing a coating in oven at 100° C. for 6hours.

The cast film was tested to characterized its relative degree ofomniphobicity, and it had the following properties: Water Contact Angle:102°; Water Sliding Angle: 25° (75 μL droplet); Oil Contact Angle: 55°(Cooking/vegetable oil); Oil Sliding Angle: 15° (5 μL droplet);Permanent Ink Resistance: 10 (in a scale of 1-10, where 10 is the bestand 1 is the worst) [Appearance: clear transparent; and ScratchResistance: 10 (in a scale of 1-10, where 10 is excellent).

This example illustrates a one-pot approach according to the disclosurefor making an omniphobic coating with several favorable properties suchas scratch resistance, permanent ink resistance, good optical clarity,and an anti-graffiti surface. In contrast to Hu et al. U.S. PublicationNo. 2016/0200937 which uses a two-step/two-pot approach in which apolysiloxane (or other hydrophobic component) is first grafted onto acopolymer with randomly distributed hydrophobic functional groups usingtoxic chemicals such as oxalyol chloride and phosgene gas, priorchemical modification of the monomer units is not required in thepresent process, thus providing a structurally distinct polymer productthat can be formed in a one-pot process that also avoids the use andseparation of the toxic grafting chemical reagents.

Example 2—Synthesis of Omniphobic Polyurethanes with Variable Polvol,Polvisocyanate Components

The following examples illustrate omniphobic coatings according to thedisclosure using a variety of different polyol and polyisocyanatecomponents.

Example 2.1: 20 mg HDI trimer biuret (UH 80; available fromSherwin-Williams) was taken in 20 mL vial and diluted with 2 mL acetone.To this solution, 2.5 mg PDMS-Diamine (dissolved in acetone) was addeddrop-wise, and the mixture was stirred for 5 minutes. Then to thissolution, 58 mg acrylic polyol (C939; available from Sherwin-Williams)was added, and the mixture was stirred at 65° C. for 2 hrs. Thissolution was cooled and diluted with 2 mL DMC. Using N₂ bubbling,acetone was removed and remaining solution was drop casted on a testsubstrate glass and cured at 120° C. in oven for 6 hrs.

Example 2.2: A coating was formed as in Example 2.1, except that 22 mgUH 80 polyisocyanate and 5 mg PDMS-Diamine were used.

Example 2.3: A coating was formed as in Example 2.1, except that 80 mgUH 80 polyisocyanate and 25 mg PDMS-Diamine were used.

Example 2.4: 50 mg HDIT (DESMODUR N 100A, trifunctional HDI trimer witha trifunctional HDI biuret was taken in 20 mL vial and diluted with 3 mLacetone. To this solution, 2.5 mg octyl isocyanate (dissolved inacetone) was added followed by dropwise addition of 5 mg PDMS-Diamine(dissolved in acetone), and the mixture was stirred for 5 minutes. Thento this solution 240 mg polyol (C939) was added, and the mixture wasstirred at 65° C. for 2 hrs. This solution was cooled and diluted with 6mL DMC. Using N₂ bubbling, acetone was removed and remaining solutionwas drop casted on a test substrate glass and cured at 120° C. in ovenfor 6 hrs. A coating Sample “A” was prepared in which the final solution(1 mL) was diluted in 1 mL DMC and drop casted and cured at 120° C. for6 hrs. A coating Sample “B” was prepared in which the final solution (1mL) was diluted in 2 mL DMC and drop casted and cured at 120° C. for 6hrs.

Example 2.5: A coating was formed as in Example 2.4, except that 5 mgoctyl isocyanate was used, and an additional coating Sample “C” wasprepared in which the final solution (1 mL) was diluted in 3 mL DMC anddrop casted and cured at 120° C. for 6 hrs.

Example 2.6: A coating was formed as in Example 2.4, except that 10 mgoctyl isocyanate was used.

Results: The films according to Examples 2.1-2.3 were very transparentwith a very thin film, having a 4-drop (˜80 μL) water sliding angle ofabout 20° and 1-drop oil (˜5 μL) sliding angle of about 20°. The filmsaccording to Examples 2.4-2.6 were not that much transparent, but theyshowed good omniphobic properties as compared to Examples 2.1-2.3.Example 2.5 had a 4-drop (˜80 μL) water sliding angle of about 20°-25°and 1-drop oil (˜5 μL) sliding angle of about 20°-25°. The other samples[examples 2.1-2.4] had a larger drop volume comparable water and oilsliding angles of about 20°-25°. Example 2.4 showed good repellency ascompare to other samples with fast sliding at ˜20°-25° with 1 drop (5μL) of oil.

Example 3—Synthesis of Omniphobic Polyurethanes with Variable PDMSComponents

The following examples illustrate omniphobic coatings according to thedisclosure using a mono-functional amine PDMS component additionallycontaining an alkyl (octyl) tail.

Example 3.1: 2.2 mL (2.3 g) HDIT (DESMODUR N 100A) was taken in 20 mLvial and diluted with 2 mL THF. To this solution, 0.05 mL (˜0.05 g)octyl-PDMS-NH₂ ([PDMS type, Mn=2655, prepared by reacting NH₂—PDMS-NH₂(Mn=2500 g/mol) with isooctyl isocyanate) was added dropwise, and themixture was stirred for 5 minutes. Then to this solution, 0.68 mL (0.69g) polyether polyol (MULTRANOL 4011) was added, and the mixture wasstirred at 60° C. for 20 min. This solution was cooled and diluted with6 mL DMC. Using N₂ bubbling, THF was removed and the remaining solutionwas drop casted on a test substrate glass and cured at 120° C. in ovenfor 6 hrs.

Example 3.2: A coating was formed as in Example 3.1, except that 2.3 mL(2.4 g) HDIT polyisocyanate and 0.02 mL (˜0.02 g) octyl-PDMS-NH₂ wereused.

Example 3.3: A coating was formed as in Example 3.1, except that 2.4 mL(2.5 g) HDIT polyisocyanate and 0.1 mL (0.1 g) octyl-PDMS-NH₂ were used.

Example 3.4: A coating was formed as in Example 3.1, except that 1.10 mL(1.15 g)HDIT polyisocyanate in acetone (i.e., instead of THF) and 50 mgoctyl-PDMS-NH₂ in acetone were used. Further, a coating Sample “A” wasprepared in which the final solution (1 mL) was diluted in 1 mL DMC anddrop casted and cured at 120° C. for 6 hrs, a coating Sample “B” wasprepared in which the final solution (1 mL) was diluted in 2 mL DMC anddrop casted and cured at 120° C. for 6 hrs, and a coating Sample “C” wasprepared in which the final solution (1 mL) was diluted in 3 mL DMC anddrop casted and cured at 120° C. for 6 hrs.

Example 3.5: A coating was formed as in Example 3.4, 2.3 mL (2.6 g) HDITpolyisocyanate in acetone, 100 mg octyl-PDMS-NH₂ in acetone, and 1.4 mL(1.4 g) MULTRANOL 4011 polyol were used.

Results: The sample coatings were transparent, showing slightly milkyappearance at aggregated coatings areas. Example 3.1 show omniphobicproperties with a 6-7 drop (120-140 μL) water sliding angle of about30°-35° and a 2-3 drop (10-15 μL) oil sliding angle of about 30°-35°.Other samples showed 10-12 drops (200-220 μL) water sliding angles ofabout 30°-35°, while oil repellency was about the same with a 2-3 drop(15-20 μL) oil sliding angle of about 30°-35°.

Example 4—Synthesis of Omniphobic Polyurethanes with Variable PDMSComponents

The following examples illustrate omniphobic coatings according to thedisclosure using a mono-functional amine PDMS component with no furtherfunctionalization (e.g., no alkyl (octyl) tail as in Example 3).

Example 4.1: 1.1 mL (1.15 g) HDIT (DESMODUR N 100A) was taken in 20 mLvial and diluted with 2 mL acetone. To this solution, 1.2 mg PDMS-NH₂dissolved in acetone (MW 1000 average, MONOAMINOPROPYL TERMINATEDPOLYDIMETHYLSILOXANE, asymmetric, 8-12 cst, GELEST) was added dropwise,and the mixture was stirred for 5 minutes. Then to this solution, 0.70mL (0.71 g) polyether polyol (MULTRANOL 4011) was added, and the mixturewas stirred at 60° C. for 1 hr. This solution was cooled and dilutedwith 6 mL DMC. Using N₂ bubbling, acetone was removed and the remainingsolution was drop casted on a test substrate glass and cured at 120° C.in oven for 6 hrs.

Example 4.2: A coating was formed as in Example 4.1, except that 1.15 mL(1.20 g) HDIT polyisocyanate and 6 mg PDMS-NH₂ were used.

Example 4.3: A coating was formed as in Example 4.1, except that 1.15 mL(1.20 g) HDIT polyisocyanate and 12 mg PDMS-NH₂ were used.

Example 4.4: A coating was formed as in Example 4.1, except that 1.25 mL(1.30 g) HDIT polyisocyanate and 24 mg PDMS-NH₂ were used.

Example 4.5: A coating was formed as in Example 4.1, except that 1.45 mL(1.51 g) HDIT polyisocyanate and 48 mg PDMS-NH₂ were used.

Example 5—Synthesis of Omniphobic Polyurethanes with Variable PDMSComponents

The following examples illustrate omniphobic coatings according to thedisclosure using a mono-functional amine PDMS component with no furtherfunctionalization, similar to Example 4 but with a higher molecularweight PDMS component.

Example 5.1: 1.1 mL (1.15 g) HDIT (DESMODUR N 100A) was taken in 20 mLvial and diluted with 2 mL acetone. To this solution, 2 mg PDMS-NH₂dissolved in acetone (MW 2000 average) (MONOAMINOPROPYL TERMINATEDPOLYDIMETHYLSILOXANE, asymmetric, 18-25 cSt, GELEST) was added dropwise,and the mixture was stirred for 5 minutes. Then to this solution, 0.7 mL(0.71 g) polyether polyol (MULTRANOL 4011) was added, and the mixturewas stirred at 60° C. for 1 hr. This solution was cooled and dilutedwith 6 mL DMC. Using N₂ bubbling, acetone was removed and the remainingsolution was drop casted on a test substrate glass and cured at 120° C.in oven for 6 hrs.

Example 5.2: A coating was formed as in Example 5.1, except that 1.15 mL(1.20 g) HDIT polyisocyanate and 10 mg PDMS-NH₂ were used.

Example 5.3: A coating was formed as in Example 5.1, except that 1.15 mL(1.20 g) HDIT polyisocyanate and 20 mg PDMS-NH₂ were used.

Example 5.4: A coating was formed as in Example 5.1, except that 1.25 mL(1.30 g) HDIT polyisocyanate and 40 mg PDMS-NH₂ were used.

Example 5.5: A coating was formed as in Example 5.1, except that 1.45 mL(1.51 g) HDIT polyisocyanate and 80 mg PDMS-NH₂ were used.

Example 6—Synthesis of Omniphobic Polyurethanes with PDMS ComponentBlends

The following examples illustrate omniphobic coatings according to thedisclosure using a blend of mono-functional amine PDMS components withno further functionalization at different ratios.

Example 6.1: 1.1 mL (1.15 g) HDIT (DESMODUR N 100A) was taken in 20 mLvial and diluted with 1 mL acetone and vortexed for less than 1 minute.To this solution, 1.2 mg PDMS-NH₂ (1K) dissolved in acetone (MW 1000average) followed by 2 mg PDMS-NH₂ (2K) dissolved in acetone (MW 2000average) were added dropwise, and the mixture was stirred for 5 minutes.Then to this solution, 0.7 mL (0.71 g) polyether polyol (MULTRANOL 4011)was added, and the mixture was stirred at 60° C. for 1 hr. This solutionwas cooled and diluted with 6 mL DMC. Using N₂ bubbling, acetone wasremoved and the remaining solution was drop casted on a test substrateglass and cured at 120° C. in oven for 6 hrs.

Example 6.2: A coating was formed as in Example 6.1, except that 6 mgPDMS-NH₂ (1K) was used.

Example 6.3: A coating was formed as in Example 6.1, except that 1.2 mL(1.25 g) HDIT polyisocyanate and 12 mg PDMS-NH₂ (1K) were used.

Example 6.4: A coating was formed as in Example 6.1, except that 1.2 mL(1.25 g) HDIT polyisocyanate and 24 mg PDMS-NH₂ (1K) were used.

Example 6.5: A coating was formed as in Example 6.1, except that 1.25 mL(1.03 g) HDIT polyisocyanate and 48 mg PDMS-NH₂ (1K) were used.

Example 6.6: A coating was formed as in Example 6.1, except that 1.2 mL(1.25 g) HDIT polyisocyanate and 80 mg PDMS-NH₂ (1K) were used.

Example 6.7: A coating was formed as in Example 6.1, except that thePDMS-NH₂ (2K) component was added before the PDMS-NH₂ (1K) component.

Example 6.8: A coating was formed as in Example 6.7, except that 10 mgPDMS-NH₂ (2K) was used.

Example 6.9: A coating was formed as in Example 6.7, except that 1.2 mL(1.25 g) HDIT polyisocyanate and 20 mg PDMS-NH₂ (2K) were used.

Example 6.10: A coating was formed as in Example 6.7, except that 1.2 mL(1.25 g) HDIT polyisocyanate and 40 mg PDMS-NH₂ (2K) were used.

Example 6.11: A coating was formed as in Example 6.7, except that 1.25mL (1.30 g) HDIT polyisocyanate and 80 mg PDMS-NH₂ (2K) were used.

Example 7—Synthesis of Omniphobic Polyurethanes with PDMS ComponentBlends

The following examples illustrate omniphobic coatings according to thedisclosure using a blend of mono-functional amine PDMS components withno further functionalization at different PDMS concentrations.

Example 7.1: 1.1 mL (1.15 g) HDIT (DESMODUR N 100A) was taken in 20 mLvial and diluted with 1 mL acetone and vortexed for less than 1 minute.To this solution, 10 mg PDMS-NH₂ (2K) dissolved in acetone (MW 2000average) followed by 6 mg PDMS-NH₂ (1K) dissolved in acetone (MW 1000average) were added dropwise, and the mixture was stirred for 5 minutes.Then to this solution, 0.7 mL (0.71 g) polyether polyol (MULTRANOL 4011)was added, and the mixture was stirred at 60° C. for 1 hr. This solutionwas cooled and diluted with 6 mL DMC. Using N₂ bubbling, acetone wasremoved and the remaining solution was drop casted on a test substrateglass and cured at 120° C. in oven for 6 hrs.

Example 7.2: A coating was formed as in Example 7.1, except that 20 mgPDMS-NH₂ (2K) and 12 mg PDMS-NH₂ (1K) were used.

Example 7.3: A coating was formed as in Example 7.1, except that 1.25 mL(1.3 g) HDIT polyisocyanate, 20 mg PDMS-NH₂ (2K), and 12 mg PDMS-NH₂(1K) were used.

Results: Samples showed sliding angles of about 15°-20° for water aswell as oil (75 μL and 15 μL droplets, respectively). Example 7.1 wasbest among these three for both water and oil.

Example 8—Synthesis of Omniphobic Polyurethanes with PDMS ComponentBlends at Various Curinq Conditions

The following examples illustrate omniphobic coatings according to thedisclosure using a blend of mono-functional amine PDMS components withno further functionalization at different ratios and curing conditions.

Example 8.1: 1.25 mL (1.30 g) HDIT (DESMODUR N 100A) was taken in 20 mLvial and diluted with 1 mL acetone and vortexed for less than 1 minute.To this solution, 20 mg PDMS-NH₂ (1K) (MW 1000 average) and 2 mgPDMS-NH₂ (2K) (MW 2000 average) both dissolved in acetone were addeddropwise, and the mixture was stirred for 5 minutes. Then to thissolution, 0.7 mL (0.71 g) polyether polyol (MULTRANOL 4011) was addedfollowed by addition of tin(II) 2-ethylhexanoate catalyst (2 drops (12mg)), and the mixture was stirred at 60° C. for 5 minutes. This solutionwas cooled and diluted with 6 mL DMC. Using N₂ bubbling, acetone wasremoved and the remaining solution was drop casted on a test substrateglass and cured at 120° C. in an oven.

Additional curing conditions were performed as follows. A coating Sample“A” was prepared as in Example 8.1, except that the coating was cured atroom temperature. A coating Sample “B” was prepared as in Example 8.1,except that the coating was cured at 50° C. A coating Sample “C” wasprepared as in Example 8.1, except that the coating was cured at 70° C.A coating Sample “D” was prepared as in Example 8.1, except that thefinal solution (1 mL) was diluted in 1 mL DMC and drop casted and curedat 120° C. for 6 hrs. A coating Sample “E” was prepared as in Example8.1, except that the final solution (1 mL) was diluted in 2 mL DMC anddrop casted and cured at 120° C. for 6 hrs.

Example 8.2: A coating was formed as in Example 8.1 (includingadditional curing samples A-E), except that 1.45 mL (1.51 g) HDITpolyisocyanate, 48 mg PDMS-NH₂ (1K), and 80 mg PDMS-NH₂ (2K) were used.

Example 8.3: A coating was formed as in Example 8.1 (includingadditional curing samples A-E), except that 1.78 mL (1.78 g) HDITpolyisocyanate, 96 mg PDMS-NH₂ (1K), and 160 mg PDMS-NH₂ (2K) were used.

Example 8.4: A coating was formed as in Example 8.1 (includingadditional curing samples A-E), except that 1.7 mL (1.9 g) HDITpolyisocyanate, 96 mg PDMS-NH₂ (1K), and 80 mg PDMS-NH₂ (2K) were used.

Example 8.5: A coating was formed as in Example 8.1 (includingadditional curing samples A-E), except that 1.45 mL (1.51 g) HDITpolyisocyanate, 96 mg PDMS-NH₂ (1K), and 40 mg PDMS-NH₂ (2K) were used.

Example 8.6: A coating was formed as in Example 8.1 (includingadditional curing samples A-E), except that 1.25 mL (1.30 g) HDITpolyisocyanate, 6 mg PDMS-NH₂ (1K), and 40 mg PDMS-NH₂ (2K) were used.

Example 8.7: A coating was formed as in Example 8.1 (includingadditional curing samples A-E), except that 1.25 mL (1.30 g) HDITpolyisocyanate, 12 mg PDMS-NH₂ (1K), and 40 mg PDMS-NH₂ (2K) were used.

Example 8.8: A coating was formed as in Example 8.1 (includingadditional curing samples A-E), except that 1.3 mL (1.36 g) HDITpolyisocyanate, 12 mg PDMS-NH₂ (1K), and 80 mg PDMS-NH₂ (2K) were used.

Example 8.9: A coating was formed as in Example 8.1 (includingadditional curing samples A-D), except that 1.25 mL (1.30 g) HDITpolyisocyanate, 2 mg PDMS-NH₂ (1K), and 20 mg PDMS-NH₂ (2K) were used.

Results: Examples 8.3, 8.3C, 8.6, 8.6C, 8.8, and 8.8C showed 10° slidingangles for water (75 μL droplet) as well as oil (15 μL droplet), but oildroplets were slowly gliding on the surface. The “B” samples cured at50° C. showed curing after 48 hrs, and showed 10°-15° sliding angles forwater (75 μL droplet) as well as oil (15 μL droplet). Example 8.8Bcoatings were best amongst all for oil repellency showing high glidingability as compared to other samples. All of the “A” samples cured atroom temp showed 20°-30° sliding angles for water (75 μL droplet) andoil (15 μL droplet) repellency.

Example 9—Synthesis of Omniphobic Polyurethanes without SolventEvaporation

The following examples illustrate omniphobic coatings according to thedisclosure using a blend of mono-functional amine PDMS components withno further functionalization at different ratios and curing conditions.

Example 9.1: Polyol (MULTRANOL 4011, 0.7 mL (0.71 g) and HDIT (1.1 mL,1.15 g) were dissolved in DMC (4 mL). The mixture heated at 70° C. for 1h. Then the solution was cooled and 1.2 mg PDMS-NH₂ (1K) dissolved in 1mL of DMC was added dropwise into it under stirring. For samples “A”,“B”, and “C”, the solutions were stirred for 2 min, 4 min, and 10 min,respectively, and then drop casted on a glass slide. Once all DMC wasevaporated, the coating was cured at 120° C. for 2.5 h. The samplesexhibited average-good optical properties (heat treatment improved theoptical properties), and good water and oil sliding angles.

Example 9.2: A coating was formed as in Example 9.1 (including samplesA-C), except that 20 mg PDMS-NH₂ (2K) was used in place of PDMS-NH₂(1K). The samples exhibited average optical properties, and good waterand oil sliding angles.

Example 9.3: A coating was formed as in Example 9.1 (including samplesA-C), except that the initial mixture was not heated at 70° C. for 1 h.The samples exhibited average-good optical properties, and good waterand oil sliding angles.

Example 9.4: A coating was formed as in Example 9.3 (including samplesA-C), except that 20 mg PDMS-NH₂ (1K) was used. The samples exhibitedaverage-good optical properties, and good water and oil sliding angles.

Example 9.5: Polyol (MULTRANOL 4011, 0.7 mL (0.71 g) and HDIT (1.1 mL,1.15 g) were dissolved in DMC (2 mL). The mixture heated at 70° C. for 1h. For sample “A”, the solution was cooled and 1.2 mg PDMS-NH₂ (1K)dissolved in 0.1 mL of acetone was added dropwise into it understirring. For sample “B”, the solution was cooled and 1.2 mg PDMS-NH₂(1K) dissolved in 0.3 mL of acetone was added dropwise into it understirring. The sample solutions were stirred for 2 min or 8 min, and thendrop casted on a glass slide. Once all DMC was evaporated, the coatingwas cured at 120° C. for 2.5 h. The samples exhibited good opticalproperties, and good water and oil sliding angles.

Example 9.6: A coating was formed as in Example 9.5 (including samplesA-B), except that the initial mixture was not heated at 70° C. for 1 h.The samples exhibited good optical properties, and good water and oilsliding angles.

Example 9.7: A coating was formed as in Example 9.5 (including samplesA-B), except that the PDMS-NH₂ (1K) was dissolved in acetone instead ofTHF. The samples exhibited good optical properties, but bad water andoil sliding angles.

Example 9.8: A coating was formed as in Example 9.7 (including samplesA-B), except that the initial mixture was not heated at 70° C. for 1 h.The samples exhibited good optical properties, but bad water and oilsliding angles.

Example 9.9: 1 mL (1.04 g) HDIT was added to 0.70 mL (0.71 g) polyol(MULTRANOL 4011) followed 1.5 mL acetone into it. Then this solution wasvortexed for about 1 minute until dissolution. To this solution, 1 drop(6 mg) of tin(II) 2-ethylhexanoate was added and stirred for 20 min atroom temperature. To this solution, 1.2 mg PDMS-NH₂ (1K) (dissolved inacetone) was added dropwise and stirred at room temp for 5 min. Then 6mL DMC was added into the mixture. Using N₂ bubbling, acetone wasremoved and the remaining solution was drop casted on a test substrateglass and cured at 120° C. in an oven.

Additional curing conditions were performed as follows. A coating Sample“A” was prepared as in Example 9.9, except that the coating was cured at70° C. A coating Sample “B” was prepared as in Example 9.9, except thatthe coating was cured at 50° C. A coating Sample “C” was prepared as inExample 9.9, except that the coating was cured at room temperature.

Example 9.10: A coating was formed as in Example 9.9 (including samplesA-C), except that 2.0 mg PDMS-NH₂ (2K) was used instead of 1.2 mgPDMS-NH₂ (1K).

Results: The results for Examples 9.9 and 9.10 were generally same asbetween samples using PDMS-NH₂ (1K) or samples using PDMS-NH₂ (2K) forsamples prepared at 70° C. The samples showed sliding angles of about15°-20° with 4 drops of water (˜80 μL) for Examples 9.9, 9.9A, 9.10 and9.10A.

Example 10—Green. One-Pot Synthesis Omniphobic Polyurethanes Coatings

The following examples illustrate a green approach for makingomniphobic, fluorine-free water-, oil- and ink-repellent polyurethanecoatings. It is a green approach because of the following improvementsover the above the method. 1) Solvent: Dimethyl carbonate (DMC) is usedas a solvent. DMC is exempted under the definition of volatile organiccompounds (VOCs) by the U.S. EPA 2009. Thus, DMC is particularlysuitable for commercial coatings produced on a large scale. 2)Temperature: No prior heating is required for casting, thus saving timeand energy. 3) Full curing of the coatings can be performed at 70-80° C.instead of 70-80 to 120° C. 4) No bubbling of VOCs (e.g., THE/acetone),for example in a solvent exchange process (i.e., which can be omittedwith the green approach). The examples illustrate the synergy ofsuitable catalyst, aprotic polar solvents such as dimethyl carbonate,and the use of reactive groups on polydimethylsiloxane, which enable theformation of optically clear films with excellent water, oil and inkrepellency. In the absence of proper catalyst, aprotic polar solvents,or reactive group on PDMS, the films are optically not very clear. Thepolyurethane coatings are readily applicable to metal, glass, wood,plastics and fabrics because of the strong adhesive properties of thepolyurethanes. The obtained coatings are durable due to the crosslinkedpolyurethane matrix and are optically clear even for relatively thickcoatings (e.g., over 100 microns, such as 100-500 microns). The coatingcompositions can be used in water-, oil-, anti-fingerprint andanti-graffiti paints.

Materials: Acetone (Fisher Thermo Scientific), Dimethyl carbonate (SigmaAldrich), Bis-(3-aminopropyl)-terminated polydimethylsiloxane(PDMS-2.5K, Mn=2500 g/mol, Sigma-Aldrich), monoaminopropyl terminatedpolydimethylsiloxane-asymmetric (PDMS-1K, Mn=1000 g/mol, Gelest. INC),monoaminopropyl terminated polydimethylsiloxane-asymmetric (PDMS-2K,Mn=2000 g/mol, Gelest. INC) were purchased and used without furtherpurification. 1,8-Diazabicyclo[5.4.0]undec-7-ene (“DBU”),1,4-Diazabicyclo[2.2.2]octane (DABCO), Tin(II) 2-ethylhexanoate (“TinII” or “Tin”) were used as received. Polypropylene oxide-based triol(Mn=300 g/mol, MULTRANOL 4011, from Covestro) and poly(hexamethylenediisocyanate) (DESMODUR N 100A from Covestro), acrylic polyol (CC939,Sherwin-Williams) and hexamethylene diisocyanate trimer (HDIT, UH80,from Sherwin-Williams) were used as received. A reducer or solventmixture (US38, Sherwin-William) is a mixture of n-butyl propionate,n-butyl acetate, ethyl n-amyl ketone, ethyl 3-ethoxy propionate, and wasused as received.

Water Sliding Angles: The water sliding angle was determined asdescribed above for a 75 μl water droplet, and the result was rated on ascale from 1 (worst) to 5 excellent):

Rating Sliding Angle 5 ≤20° 4 21-30° 3 31-50° 2 51-90° 1 No sliding orwater spread on the surface

Oil Sliding Angles: The oil sliding angle was determined as describedabove for a 10 μl oil droplet, and the result was rated on a scale from1 (worst) to 5 excellent):

Rating Sliding Angle 5 ≤15° 4 16-20° 3 21-25° 2 26-90° 1 No sliding orwater spread on the surface

Optical Properties/Transmittance or Clarity: The optical transmittance(or clarity) of a sample film was tested using a Perkin Elmer Lambda 25UV-Vis spectrometer, and the result was rated on a scale from 1 (worst)to 5 excellent), with a reference polyurethane without PDMS (or otherhydrophobic polymer) having 91% transmittance:

Optical Rating Transmittance 5 >87% 4  80-87%. 3 71-79% 2 60-70% 1 <60%

Scratch resistance and permanent ink resistance were evaluated asdescribed above.

Examples 10.1-10.12 (PDMS-2.5K): Master solution A was prepared as 500mg of PDMS (2.5K) dissolved in 5 mL THF. Master solution B was preparedas 40 mg DBU or Tin catalyst dissolved in 4 mL THF. In a 20 mL glassvial, 470 mg of polyisocyanate(UH80) and 1.88 g of polyol CC-939 weredissolved in 8 mL DMC and stirred for 30 minutes. To this solution thedesired amount of the master solution A was added dropwise understirring at room temperature. The reaction mixture was then stirred foranother 30 minutes and desired amount of catalyst was added dropwisefrom master solution B. After catalyst addition, the coating solutionwas then stirred for about 30-40 minutes (i.e., until an increasedviscosity was visually observed), and then drop cast on glass or metalslides. The coated slides were then dried in ambient condition and curedat 70° C. for 12 hours in an oven. The coating thicknesses were 140±20μm. The composition and properties of the resulting films are summarizedin Table 1 below.

TABLE 1 Composition and Performance of Examples 10.1-10.12 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 10.1 DBU/1 mg 70-80 5 5 5 10 106% 10.2 DBU/2 mg 70-80 5 5 5 10 10 6% 10.3 DBU-Tin/ 70-80 5 5 5 10 10 6%0.5 + 0.5 mg 10.4 DBU/2.5 mg 70-80 5 5 4 10 10 6% 10.5 DBU/1 mg 70-80 55 5 10 10 4% 10.6 DBU/2 mg 70-80 5 5 5 10 10 4% 10.7 DBU-Tin/ 70-80 5 55 10 10 4% 0.5 + 0.5 mg 10.8 DBU/2.5 mg 70-80 5 5 4 10 10 4% 10.9 DBU/1mg 70-80 5 5 5 10 10 2% 10.10 DBU/2 mg 70-80 5 5 5 10 10 2% 10.11DBU-Tin/ 70-80 5 5 5 10 10 2% 0.5 + 0.5 mg 10.12 Tin/1 mg 70-80 5 5 5 1010 2%

Examples 10.13-10.15 (PDMS-1K): Master solution A was prepared as 500 mgof PDMS (1K) dissolved in 5 mL THF. Master solution B was prepared as 40mg DBU or DABCO catalyst dissolved in 4 mL THF. In a 20 mL glass vial,470 mg of polyisocyanate(UH80) and 1.88 g of polyol CC-939 weredissolved in 8 mL DMC and stirred for 30 minutes. To this solution, thedesired amount of the master solution A was added dropwise understirring at room temperature. The reaction mixture was then stirred foranother 30 minutes and desired amount of catalyst was added dropwisefrom master solution B. After catalyst addition, the coating solutionwas then stirred for about 30-40 minutes (i.e., until an increasedviscosity was visually observed), and then drop cast on glass or metalslides. The coated slides were then dried in ambient condition and curedat 70° C. for 12 hours in an oven. The coating thicknesses were 140±20μm. The composition and properties of the resulting films are summarizedin Table 2 below.

TABLE 2 Composition and Performance of Examples 10.13-10.15 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 10.13 DBU/2.5 mg 70-80 5 4 5 1010 6% 10.14 DBU/5 mg 70-80 5 9 4 9 10 6% 10.15 DABCO/5 70-80 5 4 3 6 96% mg

Examples 10.16-10.18 (PDMS-2K): Master solution A was prepared as 500 mgof PDMS (2K) dissolved in 5 mL THF. Master solution B was prepared as 40mg DBU or DABCO catalyst dissolved in 4 mL THF. In a 20 mL glass vial,470 mg of polyisocyanate(UH80) and 1.88 g of polyol CC-939 weredissolved in 8 mL DMC and stirred for 30 minutes. To this solution, thedesired amount of the master solution A was added dropwise understirring at room temperature. The reaction mixture was then stirred foranother 30 minutes and desired amount of catalyst was added dropwisefrom master solution B. After catalyst addition, the coating solutionwas then stirred for about 30-40 minutes (i.e., until an increasedviscosity was visually observed), and then drop cast on glass or metalslides. The coated slides were then dried in ambient condition and curedat 70° C. for 12 hours in an oven. The coating thicknesses were 140±20μm. The composition and properties of the resulting films are summarizedin Table 3 below.

TABLE 3 Composition and Performance of Examples 10.16-10.18 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 10.16 DBU/2.5 mg 70-80 5 5 5 910 6% 10.17 DABCO/5 70-80 5 4 4 9 10 6% mg 10.18 DBU/5 mg 70-80 5 4 4 1010 6%

Examples 10.19-10.25 (PDMS-2.5K): In 2 mL DMC, 1280 mg HDIT (Desmodur N100A, 1.1 equ) were dissolved followed by drop wise addition of PDMS2.5K (50 mg dissolved in 0.1 mL DMC). The solution was stirred for 5min. Then to this solution 740 mg polyol (MULTRANOL 4011 dissolved in 2mL DMC, 1.0 equ with respect to HDIT) were added into it drop wiselyfollowed by addition of catalyst (desired amount dissolved in 0.1 mLDMC) were added into it and generally stirred overnight at roomtemperature. Examples 10.23-24 were stirred for 3 h. The resultingsolution was then drop cast and left for solvent evaporation and curedat 70-80° C. for 6 hrs. Samples were prepared at thicknesses in 271±15μm. The composition and properties of the resulting films are summarizedin Table 4 below.

TABLE 4 Composition and Performance of Examples 10.19-10.25 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 10.19 DBU/1 mg 70-80 5 5 4 5 52% 10.20 DBU/2 mg 70-80 5 5 4 5 5 2% 10.21 DBU/3 mg 70-80 5 5 4 5 5 2%10.22 DBU/4 mg 70-80 5 5 4 5 5 2% 10.23 DBU/5 mg 70-80 5 5 4 5 5 2%10.24 DBU-Tin/ 70-80 5 5 4 5 5 2% 0.5 + 0.5 mg 10.25 Tin/1 mg 70-80 5 54 5 5 2%

Examples 10.26-10.28 (PDMS-1K): In 2 mL DMC, 1280 mg HDIT (Desmodur N100A) were dissolved followed by drop wise addition of PDMS-1K (50 mgdissolved in 0.1 mL DMC). The solution was stirred for 5 min. Then tothis solution 740 mg polyol (MULTRANOL 4011 dissolved in 2 mL DMC, 1.0equ with respect to HDIT) were added into it drop wisely followed byaddition of catalyst (desired amount dissolved in 0.1 mL DMC) were addedinto it and generally stirred overnight at room temperature. Theresulting solution was then drop cast and left for solvent evaporationand cured at 70-80° C. for 6 hrs. Samples were prepared at thicknessesin 271±15 μm. The composition and properties of the resulting films aresummarized in Table 5 below.

TABLE 5 Composition and Performance of Examples 10.26-10.28 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 10.26 Tin/1 mg 70-80 5 5 4 5 52% 10.27 Tin/5 mg 70-80 5 5 4 5 5 2% 10.28 DBU-Tin/ 70-80 5 5 4 5 5 2%0.5 + 0.5 mg

Examples 10.29-10.31 (PDMS-1K): In 2 mL DMC, 1280 mg HDIT (Desmodur N100A, 1.1 equ) were dissolved followed by drop wise addition of PDMS-1K(50 mg dissolved in 0.1 mL DMC). The solution was stirred for 5 min.Then to this solution 740 mg polyol (MULTRANOL 4011 dissolved in 2 mLDMC, 1.0 equ with respect to HDIT) were added into it drop wiselyfollowed by addition of catalyst (desired amount dissolved in 0.1 mLDMC) were added into it and stirred overnight at room temperature. Theresulting solution was then drop cast and left in open air for solventevaporation and cured at 70-80° C. for 6 hrs. Samples were prepared atthicknesses in 271±15 μm. The composition and properties of theresulting films are summarized in Table 6 below.

TABLE 6 Composition and Performance of Examples 10.29-10.31 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 10.29 Tin/1 mg 70-80 5 5 4 5 52% 10.30 DBU-Tin/ 70-80 5 5 4 5 5 2% 0.5 + 0.5 mg 10.31 DBU-Tin/ 70-80 55 4 5 5 2% 0.5 + 0.5 mg

Metal Plate Coatings: Selected coating solutions from the above exampleswere also cast on metal (steel) plates of dimension 4 inch×6 inch (about10 cm×15 cm). The thicknesses were same as mentioned in their respectiveexamples. The properties of the resulting films are summarized in Table7 below.

TABLE 7 Performance of Coated Metal Plates Water Oil Ink Scratch Examplerepellency repellency Clarity resist. resist. 10.1 5 5 5 10 10 10.5 5 55 10 10 10.9 5 5 5 10 10 10.12 5 5 5 10 10 10.24 5 5 5 5 5 10.28 5 5 5 55 10.31 5 5 5 5 5 *Clarity indicates qualitative numbers based on thevisual observation of the coated plates

Examples 10.31-10.38 (PDMS-1K Spray Coatings): Master solution A wasprepared as 500 mg of PDMS (1K) dissolved in 5 mL THF. Master solution Bwas prepared as 40 mg DBU or DABCO catalyst dissolved in 4 mL THF. In a20 mL glass vial, 470 mg of polyisocyanate (UH80) and 1.88 g of polyolCC-939 were dissolved in 8 mL DMC and stirred for 30 minutes. To thissolution, the desired amount of the master solution A was added dropwiseunder stirring at room temperature. The reaction mixture was thenstirred for another 30 minutes and desired amount of catalyst was addeddropwise from master solution B. After catalyst addition, the coatingsolution was then stirred for about 30-40 minutes (i.e., until anincreased viscosity was visually observed), and then spray coated onglass or metal slides. The coated slides were then dried in ambientcondition and cured at 70° C. for 12 hours in an oven. The coatingthicknesses were 140±20 μm. The composition and properties of theresulting films are summarized in Table 8 below.

TABLE 8 Composition and Performance of Examples 10.32-10.38 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 10.32 DBU/1 mg 70 5 5 5 10 106% 10.33 DBU/1 mg 70 5 5 5 10 10 4% 10.34 DBU/1 mg 70 5 5 5 10 10 2%10.35 DBU/2.5 mg 70 5 5 5 10 10 6% 10.36 Tin/1 mg 70 5 5 5 10 10 4%10.37 Tin/1 mg 70 5 5 5 10 10 2% 10.37 DBU/2.5 mg 70 5 5 5 10 10 6%

Metal Plate Coatings (Spray): Selected coating solutions from the aboveexamples were also sprayed on metal (steel) plates of dimension 4 inch×6inch (about 10 cm×15 cm). The thicknesses were same as mentioned intheir respective examples. The properties of the resulting films aresummarized in Table 9 below.

TABLE 9 Performance of Coated Metal Plates Water Oil Ink Scratch Examplerepellency repellency Clarity resist. resist. 10.24 5 5 5 5 5 10.28 5 55 5 5 *Clarity indicates qualitative numbers based on the visualobservation of the coated plates

Example 11—Biobased Optically Clear, Water-, Oil- and Ink-RepellentFluorine-Free Polyurethane Coatings

The following examples illustrate omniphobic water-, oil- andink-repellent fluorine-free polyurethane coatings derived from partiallyor fully biobased feedstock. Biobased feedstock polyol/diol was combinedwith isocyanate (biobased or petroleum based), thus making the coatingpartially or fully biobased. These examples illustrate the synergy ofsuitable catalyst, aprotic polar solvents, and the use of reactivegroups on polydimethylsiloxane (PDMS), which ensure an optically clearfilm, with excellent water, oil and ink repellency. In the absence ofappropriate catalyst, aprotic polar solvents or reactive group on PDMS,these films are optically not clear. These polyurethane coatings can bereadily applied to metal, glass, wood, and fabrics because of the strongadhesive properties of the polyurethanes. The coatings obtained here aredurable due to the crosslinked polyurethanes matrix and are opticallyclear even for relatively thick coatings (e.g., over 100 microns, suchas 100-500 microns). Also, other polymers with amine groups such asfluorinated amine can be used instead of PDMS amine. The coatingcompositions can be can be loaded with nanofillers such as CNC, grapheneoxide, nanoclay, silica particles as well to provide self-cleaningcomposite films. The examples illustrate a cost-effective biobasedomniphobic polyurethane composition, which has favorable water-, oil-and ink-repellent properties.

Materials: Acetone (Fisher Thermo Scientific), Dimethyl carbonate (SigmaAldrich), Bis-(3-aminopropyl)-terminated polydimethylsiloxane(PDMS-2.5K, Mn=2500 g/mol, Sigma-Aldrich), monoaminopropyl terminatedpolydimethylsiloxane-asymmetric (PDMS-1K, Mn=1000 g/mol, Gelest. INC),monoaminopropyl terminated polydimethylsiloxane-asymmetric (PDMS-2K,Mn=2000 g/mol, Gelest. INC) were purchased and used without furtherpurification. Isosorbide (polyol from Aldrich), hexamethylenediisocyanate trimer (HDIT, UH80, from Sherwin-Williams), pentamethylenediisocyanate trimer (Mitsui Chemicals),1,8-Diazabicyclo[5.4.0]undec-7-ene (“DBU”),1,4-Diazabicyclo[2.2.2]octane (DABCO), and Tin(II) 2-ethylhexanoate(“Tin II” or “Tin”) were used as received.

Water sliding angle, oil sliding angle, and optical transmittance (orclarity) were determined and rated on a scale of 1-5 as described abovein general and for Example 10 (rating scale). Scratch resistance andpermanent ink resistance were evaluated as described above.

Examples 11.1-11.4 (PDMS-2K): In a 20 mL glass vial, 0.29 g ofIsosorbide was dissolved at 60° C. in 3 mL DMC and 0.5 mL acetone. Thesolution was then cooled down to room temperature. To this solution,0.65 mg polyisocyanate (DESMODUR N 100A) and 35 mg (polyol, MULTRANOL4011) were added dropwise under stirring at room temperature. Thereaction mixture was then stirred for 2 minutes and respective amount ofDBU catalyst was added. After catalyst addition, the solution wasstirred for another 2 minutes and then 0.1 mL (10 mg) of PDMS-2K mastersolution was added dropwise. The coating solution was then stirred forabout 15-20 minutes before drop casting on a glass slide. The coatedglass slides were then dried in ambient conditions and cured at 70° C.for 12 hours in an oven. The samples were prepared at thicknesses of140±10 μm. The composition and properties of the resulting films aresummarized in Table 10 below.

TABLE 10 Composition and Performance of Examples 11.1-11.4 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 11.1 DBU/5 mg 70 5 5 4 10 10 3%11.2 DBU/3.75 70 5 5 5 10 10 3% mg 11.3 DBU/2.5 mg 70 5 5 5 10 10 3%11.4 DBU/1 mg 70 5 5 5 10 10 3%

Examples 11.5-11.6 (PDMS-2K): The procedure for Examples 11.1-11.4 wasfollowed, except that pentamethylene disocyanate timer (which as a 100%biobased material) was used instead of hexamethylene disocyanate timer.The composition and properties of the resulting films are summarized inTable 11 below.

TABLE 11 Composition and Performance of Examples 11.5-11.6 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 11.5 DBU/1 mg 70 5 5 5 9 102.7% 11.6 DBU/2 mg 70 5 5 5 10 10 2.7%

Example 12—Ambient-Cured Omniphobic Polyurethane Coatings

The following examples illustrate omniphobic polyurethane coatingsprepared under ambient conditions. A suitable combination of urethanecuring catalysts, appropriate solvents, and the use of reactive groupson polydimethylsiloxane provide optically clear films with excellentwater, oil, and ink repellency. Other examples illustrate the use ofmild curing conditions (e.g., 60-80° C.), while these examplesillustrate omniphobic polyurethane coatings cured at ambient temperature(e.g., 20-30° C. or about 25° C.). The polyurethane coatings are readilyapplicable to metal, glass, wood, plastics and fabrics as varioussubstrates because of the strong adhesive properties of thepolyurethanes. The obtained coatings are durable due to the cross-linkedpolyurethanes matrix and are optically clear even for relatively thickcoatings (e.g., over 100 microns, such as 100-500 microns). The coatingcompositions can be used in water-, oil-, anti-fingerprint andanti-graffiti paints. The coating compositions can be can be loaded withnanofillers such as CNC, graphene oxide, nanoclay, silica particles aswell to provide self-cleaning composite films. The examples illustrate acost-effective ambient-curable omniphobic polyurethane composition.

Materials: Acetone (Fisher Thermo Scientific), Dimethyl carbonate (SigmaAldrich), Bis-(3-aminopropyl)-terminated polydimethylsiloxane(PDMS-2.5K, Mn=2500 g/mol, Sigma-Aldrich), monoaminopropyl terminatedpolydimethylsiloxane-asymmetric (PDMS-1K, Mn=1000 g/mol, Gelest. INC),monoaminopropyl terminated polydimethylsiloxane-asymmetric (PDMS-2K,Mn=2000 g/mol, Gelest. INC) were purchased and used without furtherpurification. 1,8-Diazabicyclo[5.4.0]undec-7-ene (“DBU”),1,4-Diazabicyclo[2.2.2]octane (DABCO), Tin(II) 2-ethylhexanoate (“TinII” or “Tin”) were used as received. Polypropylene oxide-based triol(Mn=300 g/mol, MULTRANOL 4011, from Covestro) and poly(hexamethylenediisocyanate) (DESMODUR N 100A from Covestro), acrylic polyol (CC939,Sherwin-Williams) and hexamethylene diisocyanate trimer (HDIT, UH80,from Sherwin-Williams) were used as received. A reducer or solventmixture (US38, Sherwin-William) is a mixture of n-butyl propionate,n-butyl acetate, ethyl n-amyl ketone, ethyl 3-ethoxy propionate, and wasused as received.

Water sliding angle, oil sliding angle, and optical transmittance (orclarity) were determined and rated on a scale of 1-5 as described abovein general and for Example 10 (rating scale). Scratch resistance andpermanent ink resistance were evaluated as described above.

Examples 12.1-12.4 (PDMS-2.5K): Master solution A was prepared as 500 mgof PDMS (2.5K) dissolved in 5 mL DMC. Master solution B was prepared as40 mg DBU, DABCO, or Tin catalyst dissolved in 4 mL DMC. In a 20 mLglass vial, 470 mg of polyisocyanate (UH80; 1.1 equiv.) and 1.88 g ofpolyol (CC-939; 1.0 equiv.) were dissolved in 8 mL DMC and stirred for30 minutes. To this solution the desired amount (1.5 mL for 150 mg PDMS)of the master solution A was added dropwise under stirring at roomtemperature. The reaction mixture was then stirred for another 30minutes and desired amount of catalyst was added dropwise from mastersolution B. After catalyst addition, the coating solution was thenstirred for several hours, and then drop cast on glass or metal slides.The coated slides were then dried and cured in ambient conditions. Thecoating thicknesses were 140±20 μm. The composition and properties ofthe resulting films are summarized in Table 12 below.

TABLE 12 Composition and Performance of Examples 12.1-12.4 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 12.1 DBU/1 mg ambient 5 4 5 1010 6% 12.2 DBU-Tin/ ambient 5 5 5 10 10 6% 0.5 + 0.5 mg 12.3 Tin/1 mgambient 5 5 5 10 10 6% 12.4 DABCO/5 ambient 5 4 5 10 10 6% mg

Examples 12.5-12.7 (PDMS-1K): Master solution A was prepared as 500 mgof PDMS (1K) dissolved in 5 mL DMC. Master solution B was prepared as 40mg DBU, DABCO, or Tin catalyst dissolved in 4 mL DMC. In a 20 mL glassvial, 470 mg of polyisocyanate (UH80; 1.1 equiv.) and 1.88 g of polyol(CC-939; 1.0 equiv.) were dissolved in 8 mL DMC and stirred for 30minutes. To this solution the desired amount (1.5 mL for 150 mg PDMS) ofthe master solution A was added dropwise under stirring at roomtemperature. The reaction mixture was then stirred for another 30minutes and desired amount of catalyst was added dropwise from mastersolution B. After catalyst addition, the coating solution was thenstirred for several hours, and then drop cast on glass or metal slidesafter an increased viscosity was visually observed. The coated slideswere then dried and cured in ambient conditions. The coating thicknesseswere 140±20 μm. The composition and properties of the resulting filmsare summarized in Table 13 below.

TABLE 13 Composition and Performance of Examples 12.5-12.7 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 12.5 DBU/2.5 mg ambient 5 4 510 10 6% 12.6 DBU/5 mg ambient 5 4 3 10 10 6% 12.7 DABCO/5 ambient 5 4 510 10 6% mg

Examples 12.8-12.10 (PDMS-2K): Master solution A was prepared as 500 mgof PDMS (2K) dissolved in 5 mL DMC. Master solution B was prepared as 40mg DBU, DABCO, or Tin catalyst dissolved in 4 mL DMC. In a 20 mL glassvial, 470 mg of polyisocyanate (UH80; 1.1 equiv.) and 1.88 g of polyol(CC-939; 1.0 equiv.) were dissolved in 8 mL DMC and stirred for 30minutes. To this solution the desired amount (1.5 mL for 150 mg PDMS) ofthe master solution A was added dropwise under stirring at roomtemperature. The reaction mixture was then stirred for another 30minutes and desired amount of catalyst was added dropwise from mastersolution B. After catalyst addition, the coating solution was thenstirred for several hours, and then drop cast on glass or metal slidesafter an increased viscosity was visually observed. The coated slideswere then dried and cured in ambient conditions. The coating thicknesseswere 140±20 μm. The composition and properties of the resulting filmsare summarized in Table 14 below.

TABLE 14 Composition and Performance of Examples 12.8-12.10 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 12.8 DBU/5 mg ambient 5 4 4 1010 6% 12.9 DBU/2.5 mg ambient 5 5 5 10 10 6% 12.10 DABCO/5 ambient 5 5 49 10 6% mg

Examples 12.11-12.18 (PDMS-2.5K): In 2 mL DMC, 1280 mg HDIT (DESMODUR N100A) were dissolved followed by drop wise addition of PDMS 2.5K (50 mgdissolved in 0.1 mL DMC). The solution was stirred for 5 min. Then tothis solution 740 mg polyol (MULTRANOL 4011 dissolved in 2 mL DMC) wereadded into it drop wisely followed by addition of catalyst and stirredovernight at room temperature. The resulting solution was then drop castand left for solvent evaporation and cured at room temperature for 48 h.Samples were prepared at thicknesses in 271±15 μm. The composition andproperties of the resulting films are summarized in Table 15 below.

TABLE 15 Composition and Performance of Examples 12.11-12.18 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 12.11 Tin/1 mg ambient 5 5 5 109  2% 12.12 DBU/1 mg ambient 5 5 5 10 9  2% 12.13 DBU-Tin/ ambient 5 5 510 9  2% 0.5 + 0.5 mg 12.14 DABCO/ ambient 5 5 4 10 10  2% 1 mg 12.15Tin/1 mg ambient 5 5 5 10 9 0.5% 12.16 DBU/1 mg ambient 5 5 5 10 9 0.5%12.17 DBU-Tin/ ambient 5 5 5 10 9 0.5% 0.5 + 0.5 mg 12.18 DABCO/ ambient5 5 4 10 10 0.5% 1 mg

Examples 12.19-12.22 (PDMS-1K): Examples 12.19-12.22 were prepared inthe same way as Examples 12.11-12.18, but with PDMS-1K instead ofPDMS-2.5K. Samples were prepared at thicknesses in 271±15 μm. Thecomposition and properties of the resulting films are summarized inTable 16 below.

TABLE 16 Composition and Performance of Examples 12.19-12.22 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 12.19 Tin/1 mg ambient 5 5 4 109 2% 12.20 Tin/5 mg ambient 5 5 4 10 9 2% 12.21 DBU-Tin/ ambient 5 5 410 9 2% 0.5 + 0.5 mg 12.22 No catalyst ambient 5 5 4 10 9 2%

Examples 12.23-12.26 (PDMS-2K): Examples 12.23-12.26 were prepared inthe same way as Examples 12.11-12.18, but with PDMS-2K instead ofPDMS-2.5K. Samples were prepared at thicknesses in 271±15 μm. Thecomposition and properties of the resulting films are summarized inTable 17 below.

TABLE 17 Composition and Performance of Examples 12.23-12.26 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 12.23 Tin/1 mg ambient 5 5 4 109 2% 12.24 Tin/5 mg ambient 5 5 4 10 9 2% 12.25 DBU-Tin/ ambient 5 5 410 9 2% 0.5 + 0.5 mg 12.26 No catalyst ambient 5 5 4 10 9 2%

Metal Plate Coatings: Selected coating solutions from the above exampleswere also cast on metal (steel) plates of dimension 4 inch×6 inch (about10 cm×15 cm). The thicknesses were same as mentioned in their respectiveexamples. The properties of the resulting films are summarized in Table18 below.

TABLE 18 Performance of Coated Metal Plates Water Oil Ink ScratchExample repellency repellency Clarity resist. resist. 12.2 5 5 5 10 1012.13 5 5 5 10 9 12.17 5 5 5 10 9 12.21 5 5 5 10 10 12.24 5 5 5 10 10*Clarity indicates qualitative numbers based on the visual observationof the coated plates

Metal Plate Coatings (Spray): Selected coating solutions from the aboveexamples were also sprayed on metal (steel) plates of dimension 4 inch×6inch (about 10 cm×15 cm). The thicknesses were same as mentioned intheir respective examples. The properties of the resulting films aresummarized in Table 19 below.

TABLE 19 Performance of Coated Metal Plates Water Oil Ink ScratchExample repellency repellency Clarity resist. resist. 12.2 5 5 5 10 1012.13 5 5 5 10 9 12.17 5 5 5 10 9 12.21 5 5 5 10 10 12.24 5 5 5 10 10*Clarity indicates qualitative numbers based on the visual observationof the coated plates

Examples 12.27-12.31 (PDMS-2.5K Spray Coating): Examples 12.27-12.31were prepared in the same way as Examples 12.1-12.4, but with twice theamount of solvent used (i.e., solutions were prepared at half theconcentration noted above) and with spraying of the coating solutiononto a test substrate. The composition and properties of the resultingfilms are summarized in Table 20 below.

TABLE 20 Composition and Performance of Examples 12.27-12.31 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 12.27 DBU/1 mg ambient 5 5 5 1010 6% 12.28 DBU/1 mg ambient 5 5 5 10 10 4% 12.29 DBU/1 mg ambient 5 5 510 10 2% 12.30 DBU-Tin/ ambient 5 5 5 10 10 4% 0.5 + 0.5 mg 12.31 Tin/1mg ambient 5 5 5 10 10 2%

Example 13—Solvent-Independent, Ambient-Cured Omniphobic PolyurethanesCoatings

The following examples illustrate omniphobic polyurethane coatingsprepared under ambient conditions using a variety of diluents. The useof urethane with siloxanes with different reducers/diluents ensuredoptically clear film, with excellent water, oil and ink repellency.These examples illustrate ambient temperature-cured omniphobicpolyurethane coatings using common commercial solvents such as ketones(methyl n-propyl ketone, methyl isobutyl ketone, methyl ethyl ketone),esters (n-butyl propionate, n-butyl acetate, ethyl n-amyl ketone, ethyl3-ethoxy propionate) instead of polar non-protic organic solvents suchas dimethyl carbonates. The polyurethane coatings are readily applicableto metal, glass, wood, plastics and fabrics as various substratesbecause of the strong adhesive properties of the polyurethanes. Theobtained coatings are durable due to the cross-linked polyurethanesmatrix and are optically clear even for relatively thick coatings (e.g.,over 100 microns, such as 100-500 microns). The coating compositions canbe used in water-, oil-, anti-fingerprint and anti-graffiti paints. Thecoating compositions can be can be loaded with nanofillers such as CNC,graphene oxide, nanoclay, silica particles as well to provideself-cleaning composite films. The examples illustrate a cost-effectiveambient-curable omniphobic polyurethane composition, which is compatiblewith commercial diluents/solvents, for example as commonly used incommercial paint/coating compositions.

Materials: Acetone (Fisher Thermo Scientific), Dimethyl carbonate (SigmaAldrich), Bis-(3-aminopropyl)-terminated polydimethylsiloxane(PDMS-2.5K, Mn=2500 g/mol, Sigma-Aldrich), monoaminopropyl terminatedpolydimethylsiloxane-asymmetric (PDMS-1K, Mn=1000 g/mol, Gelest. INC),monoaminopropyl terminated polydimethylsiloxane-asymmetric (PDMS-2K,Mn=2000 g/mol, Gelest. INC) were purchased and used without furtherpurification. 1,8-Diazabicyclo[5.4.0]undec-7-ene (“DBU”),1,4-Diazabicyclo[2.2.2]octane (DABCO), Tin(II) 2-ethylhexanoate (“TinII” or “Tin”) were used as received. Polypropylene oxide-based triol(Mn=300 g/mol, MULTRANOL 4011, from Covestro) and poly(hexamethylenediisocyanate) (DESMODUR N 100A from Covestro), acrylic polyol (CC939,Sherwin-Williams) and hexamethylene diisocyanate trimer (UH80, fromSherwin-Williams) were used as received. A reducer or solvent mixture(US38, Sherwin-William) is a mixture of n-butyl propionate, n-butylacetate, ethyl n-amyl ketone, ethyl 3-ethoxy propionate, and was used asreceived.

Water sliding angle, oil sliding angle, and optical transmittance (orclarity) were determined and rated on a scale of 1-5 as described abovein general and for Example 10 (rating scale). Scratch resistance andpermanent ink resistance were evaluated as described above.

Examples 13.1-13.21 (PDMS-2.5K): 1880 mg polyol CC939 and 1 mL reducer(US38) were mixed followed by the addition of PDMS 2.5K (dissolved in0.1 mL Reducer US38) drop wisely into it. Then to this solution 470 mgHDIT (UH80) (dissolved in 0.9 mL of US38) was added drop wisely into itunder continuous stirring. Then it was stirred for 5 min, followed bythe addition of catalyst (dissolved in 0.1 mL US38) were added into itand stirred for 2-6 h at room temperature. The final sample was thendrop cast on glass slide and left for solvent evaporation and then curedin oven at 70° C. for 6 hrs or dried overnight at room temperature.Coatings were prepared in the final thicknesses of 157±15 μm. Thecomposition and properties of the resulting films are summarized inTable 21 below.

TABLE 21 Composition and Performance of Examples 13.1-13.21 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.1 DBU/1 mg 70 5 5 5 10 10 2%13.2 DBU/2 mg 70 5 5 5 10 10 2% 13.3 DBU/3 mg 70 5 5 5 10 10 2% 13.4DBU/4 mg 70 5 5 5 10 10 2% 13.5 DBU/5 mg 70 5 5 5 10 10 2% 13.6 DBU-Tin/70 5 5 5 10 10 2% 0.5 + 0.5 mg 13.7 DBU-Tin/ 70 5 5 5 10 10 2% 1 + 1 mg13.8 Tin/1 mg 70 5 5 5 10 10 2% 13.9 Tin/5 mg 70 5 5 5 10 10 2% 13.10 Nocatalyst ambient 5 5 5 10 10 2% 13.11 DBU/1 mg 70 5 5 5 10 10 0.5% 13.12 DBU-Tin/ 70 5 5 5 10 10 0.5%  0.5 + 0.5 mg 13.13 DBU-Tin/ 70 5 5 510 10 0.5%  0.5 + 0.5 mg 13.14 Tin/1 mg 70 5 5 5 10 10 0.5%  13.15 Nocatalyst ambient 5 5 5 10 10 0.5%  13.16 DBU-Tin/ 70 5 5 5 10 10 4%0.5 + 0.5 mg 13.17 Tin/1 mg 70 5 5 5 10 10 4% 13.18 No catalyst ambient5 5 5 10 10 4% 13.19 DBU-Tin/ 70 5 5 5 10 10 6% 0.5 + 0.5 mg 13.20 Tin/1mg 70 5 5 5 10 10 6% 13.21 No catalyst ambient 5 5 5 10 10 6% 13.22DBU-Tin/ ambient 5 5 5 10 10 4% 0.5 + 0.5 mg 13.23 Tin/1 mg ambient 5 55 10 10 4% 13.24 No catalyst ambient 5 5 5 10 10 4%

Examples 13.25-13.36 (PDMS-1K): Examples 13.25-13.36 were prepared inthe same way as Examples 13.1-13.24, but with PDMS-1K instead ofPDMS-2.5K. Samples were prepared at thicknesses in 157±15 μm. Thecomposition and properties of the resulting films are summarized inTable 22 below.

TABLE 22 Composition and Performance of Examples 13.25-13.36 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.25 Tin/1 mg 70 5 5 4 10 10 2% 13.26 DBU-Tin/ 70 5 5 4 10 10  2% 0.5 + 0.5 mg 13.27 No catalyst 705 5 4 10 10  2% 13.28 Tin/1 mg 70 5 5 5 10 10 0.5% 13.29 DBU-Tin/ 70 5 55 10 10 0.5% 0.5 + 0.5 mg 13.30 No catalyst 70 5 5 4 10 10 0.5% 13.31Tin/1 mg ambient 5 5 4 10 10  2% 13.32 DBU-Tin/ ambient 5 5 4 10 10  2%0.5 + 0.5 mg 13.33 No catalyst ambient 5 5 4 10 10  2% 13.34 Tin/1 mgambient 5 5 5 10 10 0.5% 13.35 DBU-Tin/ ambient 5 5 5 10 10 0.5% 0.5 +0.5 mg 13.36 No catalyst ambient 5 5 4 10 10 0.5%

Examples 13.37-13.39 (PDMS-2K): Examples 13.37-13.19 were prepared inthe same way as Examples 13.1-13.24, but with PDMS-2K instead ofPDMS-2.5K. Samples were prepared at thicknesses in 157±15 μm. Thecomposition and properties of the resulting films are summarized inTable 23 below.

TABLE 23 Composition and Performance of Examples 13.37-13.39 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.37 Tin/1 mg 70 5 5 4 10 102% 13.38 DBU-Tin/ 70 5 5 4 10 10 2% 0.5 + 0.5 mg 13.39 DBU-Tin/ 70 5 5 410 10 2% 0.5 + 0.5 mg

Examples 13.40-13.47 (PDMS-2.5K): In 2 ml 2-Butanone, 1280 mg of HDIT(DESMODUR N 100A) were dissolved followed by drop wise addition of PDMS2.5K (dissolved in 0.2 mL 2-Butanone). The solution was stirred for 5min. Then to this solution 740 mg of polyol (MULTRANOL 4011 dissolved in2 mL 2-Butanone) were added into it drop wisely followed by addition ofcatalyst (dissolved in 0.1 mL 2-Butanone) were added into it and stirredovernight at room temperature. The resulting solutions were then dropcast and left for solvent evaporation and cured at room temperatureovernight (ambient cured) or at 70° C. for 6 h (oven cured). Sampleswere prepared at thicknesses in 271±15 μm. The composition andproperties of the resulting films are summarized in Table 24 below.

TABLE 24 Composition and Performance of Examples 13.40-13.47 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.40 Tin/1 mg ambient 5 5 4 1010 2% 13.41 DBU/1 mg ambient 5 5 4 10 10 2% 13.42 DBU-Tin/ ambient 5 5 410 10 2% 0.5 + 0.5 mg 13.43 No catalyst ambient 5 5 4 10 10 2% 13.44Tin/1 mg 70 5 5 4 10 10 2% 13.45 DBU/1 mg 70 5 5 4 10 10 2% 13.46DBU-Tin/ 70 5 5 4 10 10 2% 0.5 + 0.5 mg 13.47 No catalyst 70 5 5 4 10 102%

Examples 13.48-13.53 (PDMS-1K): Examples 13.48-13.53 were prepared inthe same way as Examples 13.40-13.47, but with PDMS-1K instead ofPDMS-2.5K. Samples were prepared at thicknesses in 271±15 μm. Thecomposition and properties of the resulting films are summarized inTable 25 below.

TABLE 25 Composition and Performance of Examples 13.48-13.53 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.48 Tin/1 mg ambient 5 4 4 1010 2% 13.49 DBU/1 mg ambient 5 5 4 10 10 2% 13.50 DBU-Tin/ ambient 5 5 410 10 2% 0.5 + 0.5 mg 13.51 DBU-Tin/ 70 5 5 4 10 10 2% 0.5 + 0.5 mg13.52 Tin/1 mg 70 5 5 4 10 10 2% 13.53 No catalyst 70 5 5 4 10 10 2%

Examples 13.54-13.59 (PDMS-2K): Examples 13.54-13.59 were prepared inthe same way as Examples 13.40-13.47, but with PDMS-2K instead ofPDMS-2.5K. Samples were prepared at thicknesses in 271±15 μm. Thecomposition and properties of the resulting films are summarized inTable 26 below.

TABLE 26 Composition and Performance of Examples 13.54-13.59 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.54 Tin/1 mg 70 5 4 4 10 102% 13.55 DBU/1 mg 70 5 5 4 10 10 2% 13.56 DBU-Tin/ 70 5 5 4 10 10 2%0.5 + 0.5 mg 13.57 Tin/1 mg ambient 5 5 4 10 10 2% 13.58 DBU/1 mgambient 5 5 4 10 10 2% 13.59 DBU-Tin/ ambient 5 5 4 10 10 2% 0.5 + 0.5mg

Examples 13.60-13.71 (PDMS-2.5K): Examples 13.54-13.59 were prepared inthe same way as Examples 13.40-13.47, but with PDMS-2K instead ofPDMS-2.5K. Samples were prepared at thicknesses in 271±15 μm. Thecomposition and properties of the resulting films are summarized inTable 27 below.

TABLE 27 Composition and Performance of Examples 13.60-13.71 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.60 Tin/1 mg ambient 5 5 4 1010 2% 13.61 DBU-Tin/ ambient 5 5 4 10 10 2% 0.5 + 0.5 mg 13.62 DABCO/ambient 5 5 4 10 10 2% 1 mg 13.63 No catalyst 70 5 5 4 10 10 2% 13.64Tin/1 mg 70 5 5 4 10 10 2% 13.65 DBU-Tin/ 70 5 5 4 10 10 2% 0.5 + 0.5 mg13.66 DABCO/ 70 5 5 4 10 10 2% 1 mg 13.67 No catalyst 70 5 5 4 10 10 2%13.68 Tin/1 mg 70 5 5 4 10 10 0.5%  13.69 DBU-Tin/ 70 5 5 5 10 10 0.5% 0.5 + 0.5 mg 13.70 DABCO/ 70 5 5 5 10 10 0.5%  1 mg 13.71 No catalyst 705 5 5 10 10 0.5% 

Examples 13.72-13.77 (PDMS-2.5K): Three different nano-filler mixtureswere formed: 1) Nano-clay Bentonite (Nano-B), 25 mg dissolved in 0.5 mLUS3 reducer; 2) Nano-clay surface modified with Trimethyl StearylAmmonium (Nano-T), 25 mg dissolved in 0.5 mL US3 reducer; and 3)cellulose nanocrystals (CNC), 25 mg dissolved in 0.5 mL US3 reducer.Coating procedure: In 1 g US3 reducer, 1880 mg of polyol CC-939 wasdissolved. Then to this solution 470 mg of UH80 dissolved in 0.9 g US3reducer was added dropwise, followed by addition of PDMS-2.5K (20 mg in0.1 ml US3 reducer) dropwise. It was then stirred for 15 min and thennano-fillers solution was added and stirred for 30 minutes. At thispoint, 1 mg Tin II catalyst dissolved in 0.1 mL US3 reducer was addedand stirred it for 2 hr at room/ambient temperature. After 2 hours, thesolution becomes relatively viscous and was drop casted on glass slidesand left to dry at ambient conditions. Half of the samples were cured atambient temperature and another half at 70° C. The composition andproperties of the resulting composite films are summarized in Table 28below.

TABLE 28 Composition and Performance of Examples 13.72-13.77 Water OilCuring % Sliding Sliding Scratch Example Nanofiller ° C. TransmittanceAngle Angle resist. Comment 13.72 CNC Ambient 87.4 13° 15° Excellent CNC1 wt % phase separation 13.73 CNC 70 83 11° 14° Excellent CNC 1 wt %phase separation 13.74 Nano-B Ambient 86.2 13° 17° Excellent 1 wt %13.75 Nano-B 70 86.3 10° 12° Excellent 1 wt % 13.76 Nano-T Ambient 88.413° 18° Excellent 1 wt % 13.77 Nano-T 70 88.7 11° 12° Excellent 1 wt %

Metal Plate Coatings: Selected coating solutions from the above exampleswere also cast on metal (steel) plates of dimension 4 inch×6 inch (about10 cm×15 cm). The thicknesses were same as mentioned in their respectiveexamples. The properties of the resulting films are summarized in Table29 below.

TABLE 29 Performance of Coated Metal Plates Water Oil Ink ScratchExample repellency repellency Clarity resist. resist. 13.6 5 5 5 10 1013.10 5 5 5 10 10 13.12 5 5 5 10 10 13.15 5 5 5 10 10 13.16 5 5 5 10 1013.18 5 5 5 10 10 13.24 5 5 5 10 10 *Clarity indicates qualitativenumbers based on the visual observation of the coated plates

Metal Plate Coatings (Spray): Selected coating solutions from the aboveexamples were also sprayed on metal (steel) plates of dimension 4 inch×6inch (about 10 cm×15 cm). The thicknesses were same as mentioned intheir respective examples. The properties of the resulting films aresummarized in Table 30 below.

TABLE 30 Performance of Coated Metal Plates Water Oil Ink ScratchExample repellency repellency Clarity resist. resist. 13.6 5 5 5 10 1013.12 5 5 5 10 10 13.15 5 5 5 10 10 13.18 5 5 5 10 10 *Clarity indicatesqualitative numbers based on the visual observation of the coated plates

Examples 13.78-13.81 (PDMS-2.5K Spray Coatings): Coating solutions wereprepared in the same way as above for Examples 13.1-13.21, and they weresprayed on a PVC pipe substrate. The composition and properties of theresulting films are summarized in Table 31 below.

TABLE 31 Composition and Performance of Examples 13.78-13.81 CatalystCuring Water Oil Ink Scratch PDMS Example type/amount ° C. repellencyrepellency Clarity resist. resist. wt. % 13.78 Tin/1 mg 70 5 5 5 10 104% 13.79 Tin/1 mg ambient 5 5 5 10 10 4% 13.80 Tin/1 mg 70 5 5 5 10 104% 13.81 Tin/1 mg ambient 5 5 5 10 10 4% *Clarity indicates qualitativenumbers based on the visual observation of the coated plastic

Example 14—Omniphobic Polyurethane Coatings on 3D Printed Substrates

This example illustrates omniphobic polyurethane coatings according tothe disclosure as 3D printed article substrate. Traditionally, 3Dprinting suffers three disadvantages: 1) water/liquid leakage, 2) roughsurfaces, and 3) mechanically weak, which can result from the generallyporous, rough, and matte surfaces of 3D printed materials. Objectsprinted with poly(lactic acid) (PLA) also have low mechanical strength.Application of coatings according to the disclosure on the surface of 3Dprinted objects can solve these problems, for example providing coatedmaterials having better barrier properties, smooth, shiny surface, andimproved mechanical strength.

In a 20 mL glass vial, 470 mg of isocyanate HDIT (UH80) was dissolved in2 mL reducer (US3), and 1 mL acrylic polyol CC-939 was added to it understirring. At this point, 100 mg of amino-functional PDMS dissolved in0.5 mL reducer was added dropwise to the reaction mixture. The solutionwas stirred at room temperature for about 30 minutes. After stirring,Tin(II) ethylhexanoate catalyst (2.5 mg) was added and stirred foranother 30 minutes to get appropriate viscosity. The solution was thendrop casted onto a 3D printed material surface. The coated samples werethen cured at room temperature overnight. The next day, properties ofthe coated objects were evaluated.

The coated materials were shinier than uncoated materials. The coatingsalso significantly improved barrier properties of the printed 3D objectsin comparison to the uncoated porous material. The coatings alsodemonstrated anti-smudge properties and had improved mechanicalproperties. The coatings also had improved repellency properties, with awater sliding angle of 13-14°, an oil sliding angle of 19°, and ahexadecane sliding angle of 18°.

Because other modifications and changes varied to fit particularoperating requirements and environments will be apparent to thoseskilled in the art, the disclosure is not considered limited to theexample chosen for purposes of illustration, and covers all changes andmodifications which do not constitute departures from the true spiritand scope of this disclosure.

Accordingly, the foregoing description is given for clearness ofunderstanding only, and no unnecessary limitations should be understoodtherefrom, as modifications within the scope of the disclosure may beapparent to those having ordinary skill in the art.

All patents, patent applications, government publications, governmentregulations, and literature references cited in this specification arehereby incorporated herein by reference in their entirety. In case ofconflict, the present description, including definitions, will control.

Throughout the specification, where the compositions, processes, kits,or apparatus are described as including components, steps, or materials,it is contemplated that the compositions, processes, or apparatus canalso comprise, consist essentially of, or consist of, any combination ofthe recited components or materials, unless described otherwise.Component concentrations can be expressed in terms of weightconcentrations, unless specifically indicated otherwise. Combinations ofcomponents are contemplated to include homogeneous and/or heterogeneousmixtures, as would be understood by a person of ordinary skill in theart in view of the foregoing disclosure.

What is claimed is:
 1. A method for forming a thermoset omniphobiccomposition, the method comprising: (a) reacting at least onepolyisocyanate, at least one amine-functional hydrophobic polymer havinga glass transition temperature (T_(g)) of 50° C. or less, and at leastone polyol to form a partially crosslinked reaction product; and (b)curing the partially crosslinked reaction product to form the thermosetomniphobic composition; wherein the thermoset omniphobic composition isfluorine-free.
 2. The method of claim 1, wherein the polyisocyanatecomprises a diisocyanate.
 3. The method of claim 1, wherein thepolyisocyanate comprises a triisocyanate.
 4. The method of claim 1,wherein the polyisocyanate is selected from the group consisting of1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI),hydrogenated MDI, xylene diisocyanate (XDI), tetramethylxyloldiisocyanate (TMXDI), 4,4′-diphenyl-dimethylmethane diisocyanate, di-and tetraalkyl-diphenylmethane diisocyanate, 4,4′-dibenzyldiiso-cyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,one or more isomers of tolylene diisocyanate (TDI),1-methyl-2,4-diiso-cyanatocyclohexane,1,6-diisocyanato-2,2,4-trimethyl-hexane,1,6-diisocyanato-2,4,4-trimethylhexane,1-iso-cyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinatedand brominated diisocyanates, phosphorus-containing diisocyanates,tetramethoxybutane 1,4-diisocyanate, butane 1,4-diisocyanate, hexane1,6-diisocyanate (HDI), HDI dimer (HDID), HDI trimer (HDIT), HDI biuret,dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate, ethylenediisocyanate, phthalic acid bisisocyanatoethyl ester,1-chloromethylphenyl 2,4-diisocyanate, 1-bromomethylphenyl2,6-diisocyanate, 3,3-bischloromethyl ether 4,4′-diphenyldiisocyanate,trimethylhexamethylene diisocyanate, 1,4-diisocyanato-butane,1,2-diisocyanatododecane, and combinations thereof.
 5. The method ofclaim 1, wherein the amine-functional hydrophobic polymer is selectedfrom the group consisting of amine-functional polysiloxanes,amine-functional polybutadienes, amine-functional polyisobutenes,amine-functional branched polyolefins, amine-functionalpoly(meth)acrylates and combinations thereof.
 6. The method of claim 1,wherein the amine-functional hydrophobic polymer comprises amonoamine-functional polysiloxane.
 7. The method of claim 1, wherein theamine-functional hydrophobic polymer comprises a diamine-functionalpolysiloxane.
 8. The method of claim 1, wherein: the amine-functionalhydrophobic polymer has a glass transition temperature in a range from−150° C. to 50° C.; the amine-functional hydrophobic polymer is a liquidat a temperature in a range from −20° C. to 40° C.; and theamine-functional hydrophobic polymer has a molecular weight ranging from300 to 50,000.
 9. The method of claim 1, wherein the polyol comprises adiol.
 10. The method of claim 1, wherein the polyol comprises three ormore hydroxyl groups.
 11. The method of claim 1, wherein the polyol isselected from the group consisting of polyether polyols, hydroxlated(meth)acrylate oligomers, glycerol, ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol,1,4-butanediol, neopentyl glycol, 1,6-hexanediol,1,4-cyclohexanedimethanol, glycerol, trimethylolpropane,1,2,6-hexanetriol, pentaerythritol, (meth)acrylic polyols, polyesterpolyols, polyurethane polyols, and combinations thereof.
 12. The methodof claim 1, wherein at least one of the polyisocyanate and the polyolcomprises a biobased polyisocyanate or a biobased polyol, respectively.13. The method of claim 1, wherein: the at least one polyisocyanate ispresent in an amount ranging from 10 wt. % to 90 wt. % relative to acombined amount of the at least one polyisocyanate, the at least oneamine-functional hydrophobic polymer, and the at least one polyol inpart (a); the at least one amine-functional hydrophobic polymer ispresent in an amount ranging from 0.01 wt. % to 20 wt. % relative to thecombined amount of the at least one polyisocyanate, the at least oneamine-functional hydrophobic polymer, and the at least one polyol inpart (a); and the at least one polyol is present in an amount rangingfrom 10 wt. % to 90 wt. % relative to the combined amount of the atleast one polyisocyanate, the at least one amine-functional hydrophobicpolymer, and the at least one polyol in part (a).
 14. The method ofclaim 1, further comprising: reacting at least one monoisocyanatemonomer with the at least one polyisocyanate, the at least oneamine-functional hydrophobic polymer, and the at least one polyol inpart (a).
 15. The method of claim 1, further comprising: adding one ormore additives to the at least one polyisocyanate, the at least oneamine-functional hydrophobic polymer, and the at least one polyol inpart (a); wherein the one or more additives are selected from the groupconsisting of nanoclay, graphene oxide, graphene, silicon dioxide(silica), aluminum oxide, cellulose nanocrystals, carbon nanotubes,titanium dioxide (titania), diatomaceous earth, biocides, pigments,dyes, thermoplastics, and combinations thereof.
 16. A method for forminga thermoset omniphobic composition, the method comprising: (a) reactingat least one polyisocyanate, at least one amine-functional hydrophobicpolymer having a glass transition temperature (T_(g)) of 50° C. or less,and at least one polyol to form a partially crosslinked reactionproduct; and (b) curing the partially crosslinked reaction product toform the thermoset omniphobic composition; wherein: the thermosetomniphobic composition has a water contact angle in a range from 90° to120° for a 5 μl droplet; the thermoset omniphobic composition has an oilcontact angle in a range from 1° to 65° for a 5 μl hexadecane droplet;the thermoset omniphobic composition has a water sliding angle in arange from 1° to 30° for a 75 μl droplet; and the thermoset omniphobiccomposition has an oil sliding angle in a range from 1° to 20° for a 10μl hexadecane droplet.
 17. The method of claim 1, wherein the thermosetomniphobic composition comprises: a thermoset polymer comprising acrosslinked backbone, the crosslinked backbone comprising: (i) firstbackbone segments, (ii) second backbone segments, (iii) third backbonesegments, (iv) urethane groups linking the first backbone segments andthe third backbone segments, and (v) urea groups linking the firstbackbone segments and the second backbone segments; wherein: the firstbackbone segments have a structure corresponding to at least one of aurethane reaction product and a urea reaction product from the at leastone polyisocyanate, the second backbone segments have a structurecorresponding to a urea reaction product from the at least oneamine-functional hydrophobic polymer having a glass transitiontemperature (T_(g)) of 50° C. or less, the third backbone segments havea structure corresponding to a urethane reaction product from the atleast one polyol, the urethane groups have a structure corresponding toa urethane reaction product of the polyisocyanate and the polyol, andthe urea groups have a structure corresponding to a urea reactionproduct of the polyisocyanate and the amine-functional hydrophobicpolymer.